Processes using staged hydrogen addition

ABSTRACT

This invention relates to processes using staged hydrogen addition in propylene polymerization. Using this process, broad/bi-modal MWD iPP with excellent stiffness properties and melt flow rates were produced.

PRIORITY

This application claims priority to and the benefit of U.S. Ser. No.61/896,291, filed Oct. 28, 2013.

FIELD OF THE INVENTION

This invention relates to processes using staged hydrogen addition inpropylene polymerization. Using this process, broad/bi-modal molecularweight distribution isotactic propylene polymers with excellentstiffness properties and melt flow rates are produced.

BACKGROUND OF THE INVENTION

Propylene impact copolymers are commonly used in a variety ofapplications where strength and impact resistance are desired, such asmolded and extruded parts (e.g. automobile parts, household appliances,luggage and furniture). Propylene homopolymers are often unsuitable forsuch applications because they are too brittle and have low impactresistance particularly at low temperature, whereas propylene impactcopolymers are specifically engineered for applications such as these.

A typical propylene impact copolymer contains two phases or components,a homopolymer component and a copolymer component. These two componentsare usually produced in a sequential polymerization process wherein thehomopolymer produced in a first reactor is transferred to a secondreactor where copolymer is produced and incorporated within the matrixof the homopolymer component. The copolymer component has rubberycharacteristics and provides the desired impact resistance, whereas thehomopolymer component provides overall stiffness.

Many process variables influence the resulting impact copolymer andthese have been studied and manipulated to obtain various effects. Forexample, U.S. Pat. No. 5,166,268 describes a “cold forming” process forproducing propylene impact copolymers where finished articles arefabricated at temperatures below the melting point of the preformedmaterial, in this case, the propylene impact copolymer. The describedprocess uses a propylene impact copolymer comprised of either ahomopolymer or crystalline copolymer matrix (first component) and atleast ten percent by weight of an “interpolymer” of ethylene and a smallamount of propylene (the second component). Adding comonomer to thefirst component is described as reducing its stiffness. Theethylene/propylene copolymer second component is reported to assist thefinished, cold-formed article in better maintaining its shape.

U.S. Pat. No. 5,258,464 describes propylene impact copolymers withimproved resistance to “stress whitening.” Stress whitening refers tothe appearance of white spots at points of impact or other stress. Theseotherwise conventional propylene impact copolymers have first and secondcomponents characterized by a numerical ratio of the second componentintrinsic viscosity to the first component intrinsic viscosity which isnear unity.

In U.S. Pat. No. 5,362,782, nucleating agent is added to propyleneimpact copolymers having a numerical ratio of the intrinsic viscosity ofthe copolymer rubber phase (second component) to the intrinsic viscosityof the homopolymer phase (first component) which is near unity, and anethylene content of the copolymer phase in the range of 38% to 60% byweight. These propylene, impact copolymers are described as producingarticles having good clarity as well as impact strength and resistanceto stress whitening. The nucleating agents are reported to increasestiffness and impact strength.

U.S. Pat. No. 5,250,631 describes a propylene impact copolymer having ahomopolypropylene first component and an ethylene/butene/propyleneterpolymer second component. Again, the goal is to obtain high impactstrength coupled with resistance to stress whitening.

Propylene impact copolymers are also used to produce films as describedin U.S. Pat. No. 5,948,839. The impact copolymer described in thispatent contains a conventional first component and 25 to 45 weightpercent ethylene/propylene second component having from 55 to 65 weightpercent ethylene. This impact copolymer composition has a melt flow offrom 7 to 60 dg/min. Such films are used in articles such as diapers.

More recently, efforts have been made to prepare propylene impactcopolymers using newly developed metallocene catalysis technology inorder to capitalize on the benefits such catalysts provide. Homopolymersprepared with such “single-site” catalysts often have narrow molecularweight distributions, and low extractables and a variety of otherfavorable properties associated therewith. Metallocene catalyzedcopolymers typically have narrow composition distributions in additionto narrow molecular weight distribution and low extractables.

Unfortunately, known metallocenes are not able to provide copolymercomponents with high enough molecular weight under commercially relevantprocess conditions. The resulting propylene impact copolymers tend tohave poor impact strength compared to their conventionally catalyzedcounterparts.

U.S. Pat. No. 5,990,242 approaches this problem by using anethylene/butene (or higher alpha-olefin) copolymer second component,rather than a propylene copolymer, prepared using a hafnocene typemetallocene. Such hafnium metallocenes are generally useful forproducing relatively higher molecular weight polymers, however, theiractivities are much lower than the more commonly used zirconocenes. Inany event, the second component molecular weights and intrinsicviscosities are lower than desired for good impact strength.

Other references of interest include US 2011/0034649; US 2011/0081817;WO 2007/071446; U.S. Pat. No. 6,429,250; US 2011/0160373; U.S. Pat. No.8,557,917; WO 01/32757 and U.S. Pat. No. 6,207,750.

Accordingly, there is need for new catalysts and/or processes thatproduce polypropylene materials that meet the needs for use in impactresistant applications, such as a good stiffness toughness balance.

SUMMARY OF THE INVENTION

New propylene impact copolymer compositions are presented having thebenefits of metallocene catalyzed polymers in addition to propertiesneeded for high impact strength applications. Importantly, thesepolymers can be economically produced using commercial-scale processesand conditions.

Using metallocene catalysts under two-stage hydrogen additionconditions, isotactic polypropylene (iPP) with excellent stiffnessproperties and melt flow ratios was obtained.

In one aspect, this invention relates to a process to polymerizepropylene comprising:

1) contacting propylene, optionally with a comonomer, with a catalystsystem comprising an activator and a catalyst compound represented bythe formula:

where:M is a group 4 metal;T is a bridging group;each X is, independently, an anionic leaving group;each R², R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², and R¹³ is, independently,halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, substituted germylcarbyl substituent or a—NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂ radical, wherein R′ is one of ahalogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group, providedthat R² and R⁸ may not be hydrogen;R⁴ and R¹⁰ are, independently, a substituted or unsubstituted arylgroup;2) polymerizing the propylene and optional comonomer for a time period,A;3) adding hydrogen or other chain termination agent and optionalcomonomer to the polymerization after time period A;4) polymerizing in the presence of at least 1 mmol hydrogen per mole ofpropylene for a time period, B, where time period A is at least as longas time period B and the hydrogen concentration during time period B isat least three times greater than the hydrogen concentration in timeperiod A; and5) obtaining a propylene polymer composition having:

-   -   a) at least 50 mol % propylene;    -   b) a 1% Secant flexural modulus of at least 1500 MPa;    -   c) an Mw/Mn of at least 5;    -   d) a melt flow rate of 50 dg/min or more (230° C., 2.16 kg);    -   e) a multimodal Mw/Mn; and    -   f) more than 15 and less than 200 regio defects per 10,000        propylene units.

In another aspect, the process further includes:

adding comonomer selected from ethylene and a C₄-C₄₀ olefin monomer tothe polymerization after time period B for a time period, C; and

obtaining a propylene polymer composition having:

-   -   a) at least 50 mol % propylene;    -   b) at least 1 mol % comonomer;    -   c) a 1% secant flexural modulus of at least 1500 MPa;    -   d) an Mw/Mn of at least 5;    -   e) a melt flow rate of 50 dg/min or more (230° C., 2.16 kg);    -   f) more than 15 and less than 200 regio defects per 10,000        propylene units; and    -   g) a CDBI of 50% or more.

In still another aspect, a propylene polymer composition is providedthat includes at least 50 mole % propylene, said polymer having a 1%secant flexural modulus of at least 1500 MPa, an Mw/Mn of at least 5, amelt flow rate of 50 dg/min or more, and preferably more than 15 andless than 200 regio defects per 10,000 propylene units.

In still another aspect, a propylene polymer composition is providedthat includes at least 50 mole % propylene and at least 1 mol %comonomer, said polymer having a CDBI of 50% or more, a 1% secantflexural modulus of at least 1500 MPa, an Mw/Mn of at least 5, a meltflow rate of 50 dg/min or more, and more than 15 and less than 200 regiodefects per 10,000 propylene units.

In still another aspect, a propylene polymer composition is providedthat comprises at least 50 mole % propylene, has a 1% secant flexuralmodulus of at least 1500 MPa, an Mw/Mn of at least 5, a multimodal Mw/Mnas determined by GPC-DRI, a melt flow rate of 50 dg/min or more, and anRCSV ratio (1 sec-1 to 2000 sec-1) of Y or more, where Y=38000X−1.559,and X is the melt flow rate in dg/min of the propylene polymer.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a graph of the polymer 1% Secant flexural modulus vs. meltflow rate (dg/min) of the polypropylene produced according topolymerization examples 1-6, 15 and 16.

FIG. 2 is a graph of shear viscosity versus shear rate for examples 4,6, 15, and 16.

DEFINITIONS

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inChemical and Engineering News, 63 (5), p. 27 (1985). Therefore, a “Group4 metal” is an element from Group 4 of the Periodic Table, e.g. Hf, Zrand Ti.

Unless otherwise indicated, “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W g of catalyst (cat), over a period of time of T hours; andmay be expressed by the following formula: P/(T×W) and expressed inunits of gPgcat-1 hr-1. Unless otherwise indicated, “conversion” is theamount of monomer that is converted to polymer product, and is reportedas mol % and is calculated based on the polymer yield and the amount ofmonomer fed into the reactor. Unless otherwise indicated, “catalystactivity” is a measure of how active the catalyst is and is reported asthe mass of product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For the purposes of this invention, ethylene shall beconsidered an α-olefin. An “alkyl” group is a linear, branched, orcyclic radical of carbon and hydrogen having at least one double bond.

For purposes of this specification and the claims appended thereto, whena polymer or copolymer is referred to as comprising an olefin, theolefin present in such polymer or copolymer is the polymerized form ofthe olefin. For example, when a copolymer is said to have an “ethylene”content of 35 wt % to 55 wt %, it is understood that the mer unit in thecopolymer is derived from ethylene in the polymerization reaction andsaid derived units are present at 35 wt % to 55 wt %, based upon theweight of the copolymer. A “polymer” has two or more of the same ordifferent mer units. A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. “Different” as usedto refer to mer units indicates that the mer units differ from eachother by at least one atom or are different isomerically. Accordingly,the definition of copolymer, as used herein, includes terpolymers andthe like. An oligomer is typically a polymer having a low molecularweight (such as Mn of less than 25,000 g/mol, preferably less than 2,500g/mol) or a low number of mer units (such as 75 mer units or less). An“ethylene polymer” or “ethylene copolymer” is a polymer or copolymercomprising at least 50 mole % ethylene derived units, a “propylenepolymer” or “propylene copolymer” is a polymer or copolymer comprisingat least 50 mole % propylene derived units, and so on.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise, the terms“group”, “radical”, and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be a radical, which contains hydrogen atoms and up to 100carbon atoms and which may be linear, branched, or cyclic, and whencyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3,GeR*3, SnR*3, PbR*3 and the like, or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g. F,Cl, Br, I) or halogen-containing group (e.g. CF3).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2,SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3 and the like, or where at leastone non-carbon atom or group has been inserted within the halocarbylradical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)2—, —Ge(R*)2—,—Sn(R*)2—, —Pb(R*)2— and the like, where R* is independently ahydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical. Additionally, two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH3, SiH2R*, SiHR*2, SiR*3, SiH2(OR*), SiH(OR*)2,Si(OR*)3, SiH2(NR*2), SiH(NR*2)2, Si(NR*2)3, and the like, where R* isindependently a hydrocarbyl or halocarbyl radical and two or more R* mayjoin together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH3, GeH2R*, GeHR*2, GeR*3, GeH2(OR*),GeH(OR*)2, Ge(OR*)3, GeH2(NR*2), GeH(NR*2)2, Ge(NR*2)3, and the like,where R* is independently a hydrocarbyl or halocarbyl radical and two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Polar radicals or polar groups are groups in which a heteroatomfunctionality is bonded directly to the indicated atom or atoms. Theyinclude heteroatoms of Groups 1-17 of the periodic table either alone orconnected to other elements by covalent or other interactions, such asionic, van der Waals forces, or hydrogen bonding. Examples of functionalgroups include carboxylic acid, acid halide, carboxylic ester,carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen(Group 14) analogues, alcohol and phenol, ether, peroxide andhydroperoxide, carboxylic amide, hydrazide and imide, amidine and othernitrogen analogues of amides, nitrile, amine and imine, azo, nitro,other nitrogen compounds, sulfur acids, selenium acids, thiols,sulfides, sulfoxides, sulfones, sulfonates, phosphines, phosphates,other phosphorus compounds, silanes, boranes, borates, alanes,aluminates. Functional groups may also be taken broadly to includeorganic polymer supports or inorganic support material, such as alumina,and silica. Preferred examples of polar groups include NR*2, OR*, SeR*,TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SnR*3, PbR*3 and the like, where R*is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl orsubstituted halocarbyl radical as defined above and two R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure. Alsopreferred are sulfonate radicals, S(═O)2OR*, where R* is defined asabove. Examples include SO3Me (mesylate), SO3(4-tosyl)(tosylate), SO3CF3(triflate), SO3(n-C4F9) (nonaflate) and the like.

An aryl group is defined to be a single or multiple fused ring groupwhere at least one ring is aromatic. Examples of aryl groups includephenyl, benzyl, carbozyl, naphthyl, and the like.

In using the terms “substituted cyclopentadienyl,” or “substitutedindenyl,” or “substituted aryl”, the substitution to the aforementionedis on a bondable ring position, and each occurrence is selected fromhydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polargroup. A “bondable ring position” is a ring position that is capable ofbearing a substituent or bridging substituent. For example,cyclopenta[b]thienyl has five bondable ring positions (at the carbonatoms) and one non-bondable ring position (the sulfur atom);cyclopenta[b]pyrrolyl has six bondable ring positions (at the carbonatoms and at the nitrogen atom). Thus, in relation to aryl groups, theterm “substituted” indicates that a hydrogen group has been replacedwith a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polargroup. For example, “methyl phenyl” is a phenyl group having had ahydrogen replaced by a methyl group.

In some embodiments of the invention, the hydrocarbyl radical isindependently selected from methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl,triacontynyl, butadienyl, pentadienyl, hexadienyl, heptadienyl,octadienyl, nonadienyl, and decadienyl. Also included are isomers ofsaturated, partially unsaturated and aromatic cyclic and polycyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl,dipropylphenyl, butylphenyl, dibutylphenyl, benzyl, methylbenzyl,naphthyl, anthracenyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl, norbornyl,norbornenyl, adamantyl and the like. For this disclosure, when a radicalis listed, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl and alkynyl radicals listed include all isomers includingwhere appropriate cyclic isomers, for example, butyl includes n-butyl,2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompounds having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity (PDI), is defined to be Mwdivided by Mn. Unless otherwise noted, all molecular weights (e.g., Mw,Mn, Mz) are g/mol and are determined by GPC-DRI as described below. Thefollowing abbreviations may be used herein: Me is methyl, Et is ethyl,Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Buis butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu istert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, THF or thf istetrahydrofuran, MAO is methylalumoxane, OTf istrifluoromethanesulfonate.

Room temperature (RT) is 23° C. unless otherwise indicated.

A “catalyst system” is a combination of at least one catalyst compound,at least one activator, an optional co-activator, and an optionalsupport material. For the purposes of this invention and the claimsthereto, when catalyst systems are described as comprising neutralstable forms of the components, it is well understood by one of ordinaryskill in the art that the ionic form of the component is the form thatreacts with the monomers to produce polymers.

In the description herein, the metallocene catalyst may be described asa catalyst precursor, a pre-catalyst compound, metallocene catalystcompound or a transition metal compound, and these terms are usedinterchangeably. A polymerization catalyst system is a catalyst systemthat can polymerize monomers to polymer. An “anionic ligand” is anegatively charged ligand which donates one or more pairs of electronsto a metal ion. A “neutral donor ligand” is a neutrally charged ligandwhich donates one or more pairs of electrons to a metal ion.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl moieties or substituted cyclopentadienyl moieties.

For purposes of this specification and the claims appended thereto, whenreferring polymerizing in the presence of at least X mmol hydrogen permole of propylene, the ratio is determined based upon the amounts ofhydrogen and propylene fed into the reactor. Likewise when referring toa hydrogen concentration during time period B that is at least threetimes greater than the hydrogen concentration in time period A, theconcentrations are determined by measuring the hydrogen amounts fed intothe reactor during time periods A and B.

DETAILED DESCRIPTION

In one aspect, a process to polymerize propylene is provided thatincludes:

1) contacting propylene, optionally with a comonomer, with a catalystsystem comprising an activator and a catalyst compound represented bythe formula:

where:M is a group 4 metal (preferably Hf or Zr);T is a bridging group;X is an anionic leaving group;each R², R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², and R¹³ is independently,halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, substituted germylcarbyl substituents or a—NR′₂, —SR′, —OR′, —OSiR′₃ or—PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkylgroup, or a C₆-C₁₀ aryl group, provided that R² and R⁸ may not behydrogen; andR⁴ and R¹⁰ are, independently, a substituted or unsubstituted arylgroup;2) polymerizing the propylene and optional comonomer for a time period,A, to produce Component A;3) adding hydrogen or other chain termination agent and optionalcomonomer to the polymerization after time period A;4) polymerizing in the presence of at least 1 mmol hydrogen per mole ofpropylene (preferably at least 5 mmol, preferably at least 10 mmol,preferably at least 15 mmol ppm, preferably at least 20 mmol, preferablyat least 30 mmol, preferably at least 50 mmol ppm per mol of propylene)for a time period, B, where time period A is at least as long as(preferably 1.5 times longer than) time period B and the hydrogenconcentration during time period B is at least three times greater thanthe hydrogen concentration in time period A; and5) obtaining a propylene polymer composition having:

-   -   a) at least 50 mol % propylene;    -   b) a 1% Secant flexural modulus of at least 1500 MPa (ASTM D 790        (A, 1.0 mm/min));    -   c) an Mw/Mn of at least 5 (GPC-DRI);    -   d) a melt flow rate of 50 dg/min or more (ASTM D 1238, 230° C.,        2.16 kg);    -   e) a multimodal Mw/Mn (GPC-DRI); and    -   f) more than 15 and less than 200 regio defects (defined to be        the sum of 2,1-erythro and 2,1-threo insertions and        3,1-isomerizations) per 10,000 propylene units, as determined by        ¹³C NMR.

In another aspect, the process further includes:

adding a comonomer selected from ethylene and a C₄-C₄₀ olefin monomer tothe polymerization after time period, B, for a time period, C; and

obtaining a propylene polymer composition having:

-   -   a) at least 50 mol % propylene;    -   b) at least 1 mol % comonomer (preferably at least 3 mol %);    -   c) a 1% secant flexural modulus of at least 1500 MPa;    -   d) an Mw/Mn of at least 5;    -   e) a melt flow rate of 50 dg/min or more;    -   f) more than 15 and less than 200 regio defects per 10,000        propylene units; and    -   g) a CDBI of 50% or more.

In a preferred embodiment of the invention, the catalyst systemcomprises an activator and a catalyst compound represented by theformula:

where:M is a group 4 metal, preferably Hf or Zr;T* is Si, Ge, or C;R¹⁴ and R¹⁵ are C₁-C₁₀ alkyl and can form a cyclic group;X is an anionic leaving group;each R², R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², and R¹³ is independently, ahalogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, substituted germylcarbyl substituents or a—NR′₂, —SR′, —OR′, —OSiR′₃ or—PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkylgroup, or a C₆-C₁₀ aryl group, provided that R² and R⁸ may not behydrogen; andR⁴ and R¹⁰ are, independently, a substituted or unsubstituted arylgroup.

The propylene polymer composition produced herein after time period Cmay be referred to herein as an impact copolymer, a propylene impactcopolymer, an in-reactor propylene impact copolymer, or in-reactorpropylene impact copolymer composition and such terms are usedinterchangeably herein.

The propylene polymer compositions of this invention may be preparedusing conventional polymerization processes such as a two-stage processin two reactors or a three stage process in three reactors, although itis also possible to produce these compositions in a single reactor. Eachstage may be independently carried out in either the gas solution orliquid slurry phase. For example, the first stage may be conducted inthe gas phase and the second in liquid slurry or vice versa and theoptional third stage in gas or slurry phase. Alternatively, each phasemay be the same in the various stages. The propylene polymercompositions of this invention can be produced in multiple reactors,preferably two or three, operated in series, where Component A ispreferably polymerized first in a gas phase, liquid slurry or solutionpolymerization process. Component B (the polymeric material produced inthe presence of Component A) is preferably polymerized in a secondreactor such as a gas phase or slurry phase reactor. In an alternativeembodiment, Component A can be made in at least two reactors in order toobtain fractions with varying melt flow rates.

As used herein “stage” is defined as that portion of a polymerizationprocess during which one component of the in-reactor composition,Component A or Component B (or component C, if a third stage ispresent), is produced. One or multiple reactors may be used during eachstage. The same or different polymerization process may be used in eachstage.

The stages of the processes of this invention can be carried out in anymanner known in the art, in solution, in suspension or in the gas phase,continuously or batchwise, or any combination thereof, in one or moresteps. Homogeneous polymerization processes are useful. (A homogeneouspolymerization process is defined to be a process where at least 90 wt %of the product is soluble in the reaction media.) A bulk homogeneousprocess is also useful. (A bulk process is defined to be a process wheremonomer concentration in all feeds to the reactor is 70 volume % ormore.) Alternately, no solvent or diluent is present or added in thereaction medium, (except for the small amounts used as the carrier forthe catalyst system or other additives, or amounts typically found withthe monomer; e.g., propane in propylene). In another embodiment, aslurry process is used in one or more stages. As used herein the term“slurry polymerization process” means a polymerization process where asupported catalyst is employed and monomers are polymerized on thesupported catalyst particles, and at least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent). Gas phase polymerizationprocesses are particularly preferred and can be used in one or morestages.

In a preferred embodiment, Stage A produces homopolypropylene and stageB produces homopolypropylene. In a preferred embodiment, Stage Aproduces homopolypropylene, stage B produces homopolypropylene and StageC produces propylene copolymer, such as propylene-ethylene copolymer.

If the polymerization is carried out as a suspension or solutionpolymerization, an inert solvent may be used, for example, thepolymerization may be carried out in suitable diluents/solvents.Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C4-10 alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In a preferred embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably less than 0.5 wt %, preferably less than0 wt % based upon the weight of the solvents. It is also possible to usemineral spirit or a hydrogenated diesel oil fraction as a solvent.Toluene may also be used. The polymerization is preferably carried outin the liquid monomer(s). If inert solvents are used, the monomer(s) is(are) typically metered in gas or liquid form.

In a preferred embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less,preferably 40 vol % or less, or preferably 20 vol % or less, based onthe total volume of the feedstream. Preferably, the polymerization isrun in a bulk process.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired polymers. Typical temperatures and/orpressures in any stage include a temperature greater than 30° C.,preferably greater than 50° C., preferably greater than 65° C.,preferably greater than 70° C., preferably greater than 75° C.,alternately less than 300° C., preferably less than 200° C., preferablyless than 150° C., most preferred less than 140° C.; and/or at apressure in the range of from 100 kPa to 20 MPa, about 0.35 MPa to about10 MPa, preferably from about 0.45 MPa to about 6 MPa, or preferablyfrom about 0.5 MPa to about 5 MPa.

In a typical polymerization in any stage, the run time of the reactionis up to 300 minutes, preferably in the range of from about 5 to 250minutes, or preferably from about 10 to 120 minutes. In a preferredembodiment in a continuous process the polymerization time for allstages is from 1 to 600 minutes, preferably 5 to 300 minutes, preferablyfrom about 10 to 120 minutes.

Hydrogen may be added to one, two or more reactors or reaction zones.Often hydrogen is added to control molecular weight and MFR. The overallpressure in the polymerization in each stage usually is at least about0.5 bar, preferably at least about 2 bar, most preferred at least about5 bar. Pressures higher than about 100 bar, e.g., higher than about 80bar and, in particular, higher than about 64 bar are usually notpreferred. In some embodiments, hydrogen is present in thepolymerization reaction zone at a partial pressure of from 0.001 to 100psig (0.007 to 690 kPa), preferably from 0.001 to 50 psig (0.007 to 345kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably0.1 to 10 psig (0.7 to 70 kPa).

The processes described herein have the unique aspect of reversehydrogen staging, e.g. hydrogen is introduced in the second stage inlarger quantities than in the first stage. For example, the second stagepolymerization occurs in the presence of at least 1 mmol of hydrogen permol of propylene (preferably at least 5 mmol, preferably at least 10mmol, preferably at least 15 mmol ppm, preferably at least 20 mmol,preferably at least 30 mmol, preferably at least 50 mmol ppm per mol ofpropylene) for a time period, B, where time period A, the polymerizationprior to period B, is at least as long as (preferably at least 1.1times, preferably at least 1.25, preferably at least 1.5 times,preferably at least 2 times, preferably at least 3 times, preferably atleast 4 times, preferably at least 5 times, preferably at least 10times) longer than time period B and the hydrogen concentration duringtime period B is at least three times (preferably 5 times, preferably 10times, preferably 15 times) greater than the hydrogen concentration intime period A, to produce component B.

In a preferred embodiment of the invention, time period A is 1 to 4500minutes, preferably 5 to 600 minutes, preferably 10 to 300 minutes. In apreferred embodiment of the invention, time period B is 1 to 1500minutes, preferably 5 to 600 minutes, preferably 10 to 300 minutes.

In a preferred embodiment of the invention, the hydrogen concentrationin stage A is 0 to 200 mmol of hydrogen per mol of propylene, preferably1 to 100 mmol of hydrogen per mol of propylene, preferably 5 to 50 mmolof hydrogen per mol of propylene. In a preferred embodiment of theinvention, the hydrogen concentration in stage B is 1 mmol to 200 mmolof hydrogen per mol of propylene (preferably 5 mmol to 150 mmol,preferably 10 to 100 mmol, preferably 15 mmol to 100 mmol, preferably 20mmol to 100 mmol, preferably 30 mmol to 100 mmol, preferably 50 mmol to100 mmol per mol of propylene).

In a preferred embodiment, propylene is combined with a catalyst systemas described herein for a time period A, hydrogen is added for a timeperiod B, and then comonomer is added for a time period, C. Hydrogen mayor may not be present in stage C (if present the hydrogen is preferablypresent at 1 mmol to 200 mmol of hydrogen per mol of propylene,preferably 5 mmol to 150 mmol, preferably 10 to 100 mmol) and stage Cmay be from 1 to 3500 minutes long (preferably 1 to 4500 minutes,preferably 5 to 600 minutes, preferably 10 to 300 minutes).

Polymerization processes of this invention can be carried out in each ofthe stages in a batch, semi-batch, or continuous mode. If two or morereactors (or reaction zones) are used, preferably they are combined soas to form a continuous process. Preferred polymerizations can be run atany temperature and/or pressure suitable to obtain the desired polymers.In a preferred embodiment of the invention, the process to produce thepropylene polymer composition is continuous.

In a preferred embodiment of the invention, in the first stage, A,propylene and from about 0 wt % to 15 wt % C2 and/or C4 to C20 alphaolefins (alternately 0.5 to 10 wt %, alternately 1 to 5 wt %), basedupon the weight of the monomer/comonomer feeds (and optional H2), arecontacted with the metallocene catalyst(s) described herein underpolymerization conditions to form Component A. In the first stage, themonomers preferably comprise propylene and optional comonomerscomprising one or more of ethylene and/or C4 to C20 olefins, preferablyC4 to C16 olefins, or preferably C6 to C12 olefins. The C4 to C20 olefinmonomers may be linear, branched, or cyclic. The C4 to C20 cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups. Ina preferred embodiment, the monomer in stage A is propylene and nocomonomer is present.

In a preferred embodiment of the invention, in the second stage, B,propylene and from about 0 wt % to 15 wt % C2 and/or C4 to C20 alphaolefins (alternately 0.5 to 10 wt %, alternately 1 to 5 wt %), basedupon the weight of the monomer/comonomer feeds, are contacted with themetallocene catalyst(s) described herein under polymerization conditionsto form Component B. In the second stage, the monomers preferablycomprise propylene and optional comonomers comprising one or more ofethylene and/or C4 to C20 olefins, preferably C4 to C16 olefins, orpreferably C6 to C12 olefins. The C4 to C20 olefin monomers may belinear, branched, or cyclic. The C4 to C20 cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups. In a preferredembodiment, the monomer in stage B is propylene and no comonomer ispresent.

In a preferred embodiment of the invention, in the optional third stage,the product from Stage B, and ethylene and from about 0 wt % to 50 wt %(preferably 3 wt % to 40 wt %, preferably 5 to 30 wt %), based upon theweight of the monomer/comonomer feeds, of one or more comonomers (suchas C3 to C20 alpha olefins) are contacted in the presence of themetallocene catalyst system(s) described herein and optional hydrogen,under polymerization conditions to form Component C intimately mixedwith Components A and B which preferably forms an impact copolymer. Inthe optional third stage, the monomers comprise ethylene and optionalcomonomers comprising one or more C3 to C20 olefins, preferably C4 toC16 olefins, or preferably C6 to C12 olefins. The C3 to C20 olefinmonomers may be linear, branched, or cyclic. The C3 to C20 cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups.

Alternately, in the second stage, Component A, propylene and optionallyfrom about 1 wt % to 15 wt % (preferably 3 wt % to 10 wt %), based uponthe weight of the monomer/comonomer feeds, of one or more comonomers(such as ethylene or C4 to C20 alpha olefins) are contacted in thepresence of the metallocene catalyst system(s) described herein andhydrogen, under polymerization conditions to form Component B intimatelymixed with Component A which forms the propylene polymer composition. Inthe second stage, the optional comonomers may comprise one or more ofethylene and C3 to C20 olefins, preferably C4 to C16 olefins, orpreferably C6 to C12 olefins. The C4 to C20 olefin monomers may belinear, branched, or cyclic. The C4 to C20 cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups.

Alternately, in the second stage, Component A and propylene arecontacted in the presence of the metallocene catalyst system(s)described herein and hydrogen, under polymerization conditions to formComponent B intimately mixed with Component A which forms the propylenepolymer composition.

The catalyst systems used in the stages may be the same or different andare preferably the same. In a preferred embodiment of the invention, thecatalyst system used in Stage A is transferred with the polymerizate(e.g. Component A) to Stage B, where it is contacted with additionalmonomer to form Component B, and thus the final propylene polymercomposition. In other embodiments of the invention, catalyst is providedto one, two or all three reaction zones.

In a preferred embodiment of the invention, Stage A produces ahomopolypropylene, stage B produces a homopolypropylene and Stage Cproduces a copolymer of ethylene-butene, ethylene-hexene,ethylene-octene, ethylene-propylene, ethylene-propylene-butene,ethylene-propylene-hexene, or ethylene-propylene-octene.

In an embodiment of the invention, little or no scavenger is used in thepolymerization in any stage to produce the polymer, i.e. scavenger (suchas trialkyl aluminum) is present at zero mol %, alternately thescavenger is present at a molar ratio of scavenger metal to transitionmetal of less than 100:1, preferably less than 50:1, preferably lessthan 15:1, preferably less than 10:1.

Other additives may also be used in the polymerization in any stage, asdesired, such as one or more scavengers, promoters, modifiers, chaintransfer agents (such as diethyl zinc), reducing agents, oxidizingagents, hydrogen, aluminum alkyls, or silanes.

In a preferred embodiment of the invention, the polymerization occurs ineither stage in a supercritical or supersolution state as described inU.S. Pat. No. 7,812,104, incorporated by reference.

In an embodiment of the invention, the productivity of the catalystsystem in a single stage or in all stages combined is at least 50gpolymer/g (cat)/hour, preferably 500 or more gpolymer/g (cat)/hour,preferably 5000 or more gpolymer/g (cat)/hour, preferably 50,000 or moregpolymer/g (cat)/hour.

In an embodiment of the invention, the activity of the catalyst systemin a single stage or in all stages combined is at least 50 kgP/molcat,preferably 500 or more kgP/molcat, preferably 5000 or more kgP/molcat,preferably 50,000 or more kgP/molcat.

In another embodiment of the invention, the conversion of olefin monomeris at least 10%, based upon polymer yield and the weight of the monomerentering the reaction zone, preferably 20% or more, preferably 30% ormore, preferably 50% or more, preferably 80% or more. A “reaction zone”,also referred to as a “polymerization zone,” is a vessel where thepolymerization process takes place, for example, a batch reactor. Whenmultiple reactors are used in either series or parallel configuration,each reactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In preferred embodiments, the polymerization occursin two, three, four or more reaction zones. In another embodiment of theinvention, the conversion of olefin monomer is at least 10%, based uponpolymer yield and the weight of the monomer entering all reaction zones,preferably 20% or more, preferably 30% or more, preferably 50% or more,preferably 80% or more.

Monomers

Monomers useful herein include substituted or unsubstituted C2 to C40alpha olefins, preferably C2 to C20 alpha olefins, preferably C2 to C12alpha olefins, preferably ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.In a preferred embodiment, the monomer comprises propylene and optionalcomonomer(s) comprising one or more of ethylene or C4 to C40 olefins,preferably C4 to C20 olefins, or preferably C6 to C12 olefins. The C4 toC40 olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀cyclic olefins may be strained or unstrained, monocyclic or polycyclic,and may optionally include heteroatoms and/or one or more functionalgroups. In a preferred embodiment of the invention, the monomer ispropylene and no comonomer is present.

Exemplary C2 to C40 olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, preferablynorbornene, norbornadiene, and dicyclopentadiene.

In a preferred embodiment, one or more dienes are present in the polymerproduced herein at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C4 to C30, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Preferably, the polymerization or copolymerization is carried out usingolefins such as ethylene, propylene, 1-butene, 1-hexene,4-methyl-1-pentene, and 1-octene, vinylcyclohexane, norbornene andnorbornadiene. In particular, propylene and ethylene are polymerized.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C4 raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

In preferred embodiments, the monomers comprise 0 wt % diene monomer inany stage, preferably in all stages.

Preferably, the comonomer(s) are present in the final propylene polymercomposition at less than 50 mol %, preferably from 0.5 to 45 mol %,preferably from 1 to 30 mol %, preferably from 3 to 25 mol %, preferablyfrom 5 to 20 mol %, preferably from 7 to 15 mol %, with the balance ofthe copolymer being made up of the main monomer (e.g. propylene).

In a preferred embodiment of the invention, the polymer produced instage A is isotactic polypropylene, preferably isotactichomopolypropylene and the polymer produced in stage B comprisespropylene and from 0.5 to 50 mol % (preferably from 0.5 to 45 mol %,preferably from 1 to 30 mol %, preferably from 3 to 25 mol %, preferablyfrom 5 to 20 mol %, preferably from 7 to 15 mol %, with the balance ofthe copolymer being made up of propylene) of ethylene or C4 to C20 alphaolefin, preferably ethylene and butene, hexene and or octene.

In a preferred embodiment of the invention, the polymer produced instage A is isotactic polypropylene, preferably isotactichomopolypropylene, and the polymer produced in stage B is an isotacticpolypropylene.

In a preferred embodiment of the invention, the polymer produced instage A is isotactic polypropylene, preferably isotactichomopolypropylene, and the polymer produced in stage B is an isotacticpolypropylene, and the polymer produced in stage C comprises propyleneand from 0.5 to 50 mol % (preferably from 0.5 to 45 mol %, preferablyfrom 1 to 30 mol %, preferably from 3 to 25 mol %, preferably from 5 to20 mol %, preferably from 7 to 15 mol %, with the balance of thecopolymer being made up of propylene) of ethylene and butene, orethylene and hexene, or ethylene and octene.

Metallocene Catalyst Compounds

Metallocene catalyst compounds useful in the processes described hereininclude those catalyst compounds represented by the formula:

where:M is a group 4 metal (preferably Hf, Ti, Zr, preferably Hf or Zr);T is a bridging group;X is an anionic leaving group;each R², R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², and R¹³ is independently,halogen atom, hydrogen, a hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, substituted germylcarbyl substituents or a—NR′₂, —SR′, —OR′, —OSiR′₃ or—PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkylgroup, or a C₆-C₁₀ aryl group, provided that R² and R⁸ may not behydrogen; andR⁴ and R¹⁰ are, independently, a substituted or unsubstituted arylgroup.

In a preferred embodiment of the invention, M is Hf or Zr; T isrepresented by the formula, (R*2G)g, where each G is C, Si, or Ge, g is1 or 2, and each R* is, independently, hydrogen, halogen, C1 to C20hydrocarbyl or a C1 to C20 substituted hydrocarbyl, and two or more R*can form a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system; X is an anionic leaving group;each R3, R5, R6, R7, R9, R11, R12, and R13 is independently, hydrogen, ahydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, orsubstituted germylcarbyl substituents, provided that R2 and R8 areindependently a C₁ to C₂₀ hydrocarbyl group; and R4 and R10 are,independently, a substituted or unsubstituted aryl, preferably asubstituted or unsubstituted phenyl group.

In any embodiment of the invention in any embodiment of any formuladescribed herein, M is Zr or Hf.

In any embodiment of the invention in any embodiment of any formuladescribed herein, each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes,amines, phosphines, ethers, and a combination thereof, (two X's may forma part of a fused ring or a ring system), preferably each X isindependently selected from halides and C1 to C5 alkyl groups,preferably each X is a methyl group.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, each R3, R5, R6, R7, R9, R11, R12, or R13 is,independently, hydrogen or a substituted hydrocarbyl group orunsubstituted hydrocarbyl group, or a heteroatom, preferably hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

In a preferred embodiment of any formula described herein, each R3, R4,R5, R6, R7, R9, R10, R11, R12, or R13 is, independently selected fromhydrogen, methyl, ethyl, phenyl, benzyl, cyclobutyl, cyclopentyl,cyclohexyl, naphthyl, anthracenyl, carbazolyl, indolyl, pyrrolyl,cyclopenta[b]thiopheneyl, fluoro, chloro, bromo, iodo and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methylphenyl,dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl,dipropylphenyl, butylphenyl, dibutylphenyl, methylbenzyl,methylpyrrolyl, dimethylpyrrolyl, methylindolyl, dimethylindolyl,methylcarbazolyl, dimethylcarbazolyl, methylcyclopenta[b]thiopheneyldimethylcyclopenta[b]thiopheneyl.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, T is a bridging group and comprises Si, Ge, orC, preferably T is dialkyl silicon or dialkyl germanium, preferably T isdimethyl silicon.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, T is a bridging group and is represented byR′2C, R′2Si, R12Ge, R′2CCR′2, R′2CCR′2CR′2, R′2CCR′2CR′2CR′2, R′C═CR′,R′C═CR′CR′2, R′2CCR′═CR′CR′2, R′C═CR′CR′═CR′, R′C═CR′CR′2CR′2,R′2CSiR′2, R′2SiSiR′2, R2CSiR′2CR′2, R′2SiCR′2SiR′2, R′C═CR′SiR′2,R′2CGeR′2, R12GeGeR′2, R′2CGeR′2CR′2, R12GeCR′2GeR′2, R′2SiGeR′2,R′C═CR′GeR′2, R′B, R′2C—BR′, R′2C—BR′—CR′2, R′2C—O—CR′2,R′2CR′2C—O—CR′2CR′2, R′2C—O—CR′2CR′2, R′2C—O—CR′═CR′, R′2C—S—CR′2,R′2CR′2C—S—CR′2CR′2, R′2C—S—CR′2CR′2, R′2C—S—CR′═CR′, R′2C—Se—CR′2,R′2CR′2C—Se—CR′2CR′2, R′2C—Se—CR2CR′2, R′2C—Se—CR′═CR′, R′2C—N═CR′,R′2C—NR′—CR′2, R′2C—NR′—CR′2CR′2, R′2C—NR′—CR′═CR′,R′2CR′2C—NR′—CR′2CR′2, R′2C—P═CR′, or R′2C—PR′—CR′2 where each R′ is,independently, hydrogen or a C1 to C20 containing hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbylor germylcarbyl substituent and optionally two or more adjacent R¹ mayjoin to form a substituted or unsubstituted, saturated, partiallyunsaturated or aromatic, cyclic or polycyclic substituent. Preferably, Tis CH2, CH2CH2, C(CH3)₂, SiMe2, SiPh2, SiMePh, silylcyclobutyl(Si(CH2)₃), (Ph)₂C, (p-(Et)₃SiPh)₂C, cyclopentasilylene (Si(CH2)₄), orSi(CH2)₅.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, each R2 and R8, is independently, a C₁ to C₂₀hydrocarbyl, or a C1 to C20 substituted hydrocarbyl, C1 to C20halocarbyl, C1 to C20 substituted halocarbyl, C1 to C20 silylcarbyl, C1to C20 substituted silylcarbyl, C1 to C20 germylcarbyl, or C1 to C20substituted germylcarbyl substituents. Preferably, each R2 and R8, isindependently, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, docedyl or an isomer thereof, preferablycyclopropyl, cyclohexyl, (1-cyclohexyl methyl)methyl, isopropyl, and thelike.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, R4 and R10 are, independently, a substitutedor unsubstituted aryl group. Preferred substituted aryl groups includearyl groups where a hydrogen has been replaced by a hydrocarbyl, or asubstituted hydrocarbyl, halocarbyl, substituted halocarbyl,silylcarbyl, substituted silylcarbyl, germylcarbyl, or substitutedgermylcarbyl substituents, a heteroatom or heteroatom containing group.

Examples of aryl and substituted aryl groups include phenyl, naphthyl,anthraceneyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl,2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl,2,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl,3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl,2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl,3,5-diethylphenyl, 3-isopropylphenyl, 4-isopropylphenyl,3,5-di-isopropylphenyl, 2,5-di-isopropylphenyl, 2-tert-butylphenyl,3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl,2,5-di-tert-butylphenyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, carbazolyl, indolyl, pyrrolyl, and cyclopenta[b]thiopheneyl.Preferred aryl groups include phenyl, benzyl, carbozyl, naphthyl, andthe like.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, R2 and R8 are a C1 to C20 hydrocarbyl, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, docedyl or an isomer thereof, preferably cyclopropyl,cyclohexyl, (1-cyclohexyl methyl)methyl, or isopropyl; and R4 and R10are independently selected from phenyl, naphthyl, anthraceneyl,2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl,3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl,2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl,4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl,2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl,3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl,2,5-di-isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl,4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,5-di-tert-butylphenyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, carbazolyl, indolyl,pyrrolyl, cyclopenta[b]thiopheneyl. In a preferred embodiment, R2, R8,R4 and R10 are as described in the preceding sentence and R3, R5, R6,R7, R9, R11, R12, and R13 are hydrogen.

Metallocene compounds that are particularly useful in this inventioninclude one or more of:

dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)zirconium dichloride;dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)hafnium dichloride;dimethylsilylene-bis(2-methyl-4-phenylindenyl)zirconium dichloride;dimethylsilylene-bis(2-methyl-4-phenylindenyl)hafnium dichloride;dimethylsilylene-bis(2-methyl-4-orthobiphenylindenyl)hafnium dichloride;dimethylsilylene-bis(2-methyl-4-orthobiphenylindenyl)zirconiumdichloride;dimethylsilylene-(2-cyclopropyl-4-orthobiphenylindenyl)(2-methyl-4-3′,5′-di-t-butylphenylindenyl)hafniumdichloride;dimethylsilylene-(2-cyclopropyl-4-orthobiphenylindenyl)(2-methyl-4-3′,5′-di-t-butylphenylindenyl)zirconiumdichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenylindenyl)zirconium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenylindenyl)hafnium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl,4-t-butylindenyl)zirconium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl,4-t-butylindenyl)hafnium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenylindacenyl)zirconiumdichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenylindacenyl)hafniumdichloride; dimethylsilylene(4-o-Biphenyl-2-(1-methylcyclohexyl)methyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)zirconiumdichloride; and dimethylsilylene(4-o-Biphenyl-2-(1-methylcyclohexyl)methyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)hafniumdichloride;where, in alternate embodiments, the dichloride in any of the compoundslisted above may be replaced with dialkyl (such as dimethyl), dialkaryl,diflouride, diiodide, or dibromide, or a combination thereof.

In a preferred embodiment of the invention, at least 50 wt %, preferablyat least 60 wt %, at least 70 wt %, preferably at least 80 wt %, atleast 90 wt % of the catalyst compound is in the rac form, based uponthe weight of the rac and meso forms present, preferably from 60 to 100wt %, preferably from 80 to 100 wt %, preferably from 90 to 100 wt %. Ina preferred embodiment of the invention, the molar ratio of rac to mesoin the catalyst compound is from 1:1 to 100:1, preferably 5:1 to 90:1,preferably 7:1 to 80:1, preferably 5:1 or greater, or 7:1 or greater, or20:1 or greater, or 30:1 or greater, or 50:1 or greater.

In an embodiment of the invention, the metallocene catalyst comprisesgreater than 55 mol % of the racemic isomer, or greater than 60 mol % ofthe racemic isomer, or greater than 65 mol % of the racemic isomer, orgreater than 70 mol % of the racemic isomer, or greater than 75 mol % ofthe racemic isomer, or greater than 80 mol % of the racemic isomer, orgreater than 85 mol % of the racemic isomer, or greater than 90 mol % ofthe racemic isomer, or greater than 92 mol % of the racemic isomer, orgreater than 95 mol % of the racemic isomer, or greater than 98 mol % ofthe racemic isomer, based on the total amount of the racemic and mesoisomer-if any, formed. In a particular embodiment of the invention, thebridged bis(indenyl)metallocene transition metal compound formedconsists essentially of the racemic isomer.

Amounts of rac and meso isomers are determined by proton NMR. ¹H NMRdata are collected at 23° C. in a 5 mm probe using a 400 MHz Brukerspectrometer with deuterated methylene chloride. (Note that some of theexamples herein use deuterated benzene, but for purposes of the claims,methylene chloride shall be used.) Data is recorded using a maximumpulse width of 45°, 5 seconds between pulses and signal averaging 16transients. The spectrum is normalized to protonated methylene chloridein the deuterated methylene chloride, which is expected to show a peakat 5.32 ppm.

In a preferred embodiment in any of the processes described herein, onemetallocene catalyst compound is used, e.g. the metallocene catalystcompounds are not different. For purposes of this invention onemetallocene catalyst compound is considered different from another ifthey differ by at least one atom. For example, “bisindenyl zirconiumdichloride” is different from (indenyl)(2-methylindenyl)zirconiumdichloride” which is different from “(indenyl)(2-methylindenyl)hafniumdichloride.” Metallocene catalyst compounds that differ only by isomerare considered the same for purposes of determining whether they are the“same”, e.g., rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl isconsidered to be the same as meso-dimethylsilylbis(2-methyl4-phenyl)hafnium dimethyl. In a preferred embodiment, the hafnium bisindenyl metallocene compound used herein is at least 90% rac isomer.

In some embodiments, two or more different metallocene catalystcompounds are present in the catalyst system used herein. In someembodiments, two or more different metallocene catalyst compounds arepresent in the reaction zone where the process(es) described hereinoccur. When two transition metal compound based catalysts are used inone reactor as a mixed catalyst system, the two transition metalcompounds should be chosen such that the two are compatible. A simplescreening method such as by 1H or 13C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible. It is preferable to use the same activator forthe transition metal compounds, however, two different activators, suchas two non-coordination anions, a non-coordinating anion activator andan alumoxane, or two different alumoxanes can be used in combination. Ifone or more transition metal compounds contain an X ligand which is nota hydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane(or other alkylating agent) is typically contacted with the transitionmetal compounds prior to addition of the non-coordinating anionactivator.

The two transition metal compounds (pre-catalysts) may be used in anyratio. Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, alternatively 1:1 to 75:1, and alternatively5:1 to 50:1. The particular ratio chosen will depend on the exactpre-catalysts chosen, the method of activation, and the end productdesired. In a particular embodiment, when using the two pre-catalysts,where both are activated with the same activator, useful mole percents,based upon the molecular weight of the pre-catalysts, are 10 to 99.9% Ato 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B,alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% Ato 1 to 10% B.

Methods to Prepare the Metallocene Compounds

Generally metallocenes are synthesized as shown below (Scheme 1) where(i) is a deprotonation via a metal salt of alkyl anion (e.g. nBuLi) toform an indenide. (ii) reaction of indenide with an appropriate bridgingprecursor (e.g. Me2SiCl2). (iii) reaction of the above product withAgOTf. (iv) reaction of the above triflate compound with anotherequivalent of indenide. (v) double deprotonation via an alkyl anion(e.g. nBuLi) to form a dianion (vi) reaction of the dianion with a metalhalide (e.g. ZrCl4). The final products are obtained byrecrystallization of the crude solids.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R1)-O— sub-units, where R1 is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underpatent number U.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst compound (per metal catalytic site). Theminimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternatepreferred ranges include from 1:1 to 500:1, alternately from 1:1 to200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mole %, alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to a cation or which is only weakly coordinated to acation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible, stabilize the transition metal cation in the sense ofbalancing its ionic charge at +1, and yet retain sufficient lability topermit displacement during polymerization.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boronmetalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides,alkoxy, and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferredare alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and arylgroups having 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, naphthyl, or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. A preferredneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994; all of which are herein fullyincorporated by reference.

Preferred compounds useful as an activator in the process of thisinvention comprise a cation, which is preferably a Bronsted acid capableof donating a proton, and a compatible non-coordinating anion whichanion is relatively large (bulky), capable of stabilizing the activecatalyst species (the Group 4 cation) which is formed when the twocompounds are combined and said anion will be sufficiently labile to bedisplaced by olefinic, diolefinic and acetylenically unsaturatedsubstrates or other neutral Lewis bases, such as ethers, amines, and thelike. Two classes of useful compatible non-coordinating anions have beendisclosed in EP 0 277 003 A1, and EP 0 277 004 A1: 1) anioniccoordination complexes comprising a plurality of lipophilic radicalscovalently coordinated to and shielding a central charge-bearing metalor metalloid core; and 2) anions comprising a plurality of boron atomssuch as carboranes, metallacarboranes, and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and are preferably represented by thefollowing formula (I):(Z)_(d) ⁺(A^(d−))  (1)wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewisbase; H is hydrogen; (L-H)+ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)d+, the cationcomponent may include Bronsted acids such as protonated Lewis basescapable of protonating a moiety, such as an alkyl or aryl, from thebulky ligand metallocene containing transition metal catalyst precursor,resulting in a cationic transition metal species. Preferably, theactivating cation (L-H)d+ is a Bronsted acid, capable of donating aproton to the transition metal catalytic precursor resulting in atransition metal cation, including ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof, preferably ammoniums of methylamine,aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,phosphoniums from triethylphosphine, triphenylphosphine, anddiphenylphosphine, oxoniums from ethers, such as dimethyl ether diethylether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid it is preferably represented by theformula: (Ar3C+), where Ar is aryl or aryl substituted with aheteroatom, a C1 to C40 hydrocarbyl, or a substituted C1 to C40hydrocarbyl, preferably the reducible Lewis acid is represented by theformula: (Ph3C+), where Ph is phenyl or phenyl substituted with aheteroatom, a C1 to C40 hydrocarbyl, or a substituted C1 to C40hydrocarbyl. In a preferred embodiment, the reducible Lewis acid istriphenyl carbenium.

The anion component Ad− includes those having the formula [Mk+Qn]d−,wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6, preferably 3, 4, 5 or6; n−k=d; M is an element selected from Group 13 of the Periodic Tableof the Elements, preferably boron or aluminum; and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having upto 20 carbon atoms with the proviso that in not more than one occurrenceis Q a halide, and two Q groups may form a ring structure. Preferably,each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms,more preferably each Q is a fluorinated aryl group, and most preferablyeach Q is a pentafluoryl aryl group. Examples of suitable Ad− componentsalso include diboron compounds as disclosed in U.S. Pat. No. 5,447,895,which is fully incorporated herein by reference.

NCA activators represented by the formula (3) may also be used herein:R_(n)M**(ArNHal)_(4-n)  (3)where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 3also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, preferably the cation is Z_(d)+ as described above.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula 3 described above, R is selected from the groupconsisting of substituted or unsubstituted C1 to C30 hydrocarbylaliphatic or aromatic groups, where substituted means that at least onehydrogen on a carbon atom is replaced with a hydrocarbyl, halide,halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid,dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C4 to C20 hydrocarbyl groups; —SR1, —NR22, and —PR32,where each R1, R2, or R3 is independently a substituted or unsubstitutedhydrocarbyl as defined above; or a C1 to C30 hydrocarbyl substitutedorganometalloid.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula 3 described above, the NCA also comprises cationcomprising a reducible Lewis acid represented by the formula: (Ar3C+),where Ar is aryl or aryl substituted with a heteroatom, a C1 to C40hydrocarbyl, or a substituted C1 to C40 hydrocarbyl, preferably thereducible Lewis acid represented by the formula: (Ph3C+), where Ph isphenyl or phenyl substituted with a heteroatom, a C1 to C40 hydrocarbyl,or a substituted C1 to C40 hydrocarbyl.

In a preferred embodiment in any of the NCA's comprising an anionrepresented by Formula 3 described above, the NCA also comprises acation represented by the formula, (L-H)d+, wherein L is an neutralLewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or3, preferably (L-H)d+ is a Bronsted acid selected from ammoniums,oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879.

Another activator useful herein comprises a salt of a cationic oxidizingagent and a noncoordinating, compatible anion represented by the formula(4):(OX^(e+))_(d)(A^(d−))_(e)  (4)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Preferred embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

In another embodiment, amidinate catalyst compounds described herein canbe used with Bulky activators. A “Bulky activator” as used herein refersto anionic activators represented by the formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group);wherein R₂ and R₃ can form one or more saturated or unsaturated,substituted or unsubstituted rings (preferably R₂ and R₃ form aperfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3 Vs, where Vs is the scaledvolume. Vs is the sum of the relative volumes of the constituent atoms,and is calculated from the molecular formula of the substituent usingthe following table of relative volumes. For fused rings, the Vs isdecreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

MV Per Total MV Activator substituent (Å³) (Å³) Dimethylanilinium 2611044 tetrakis(perfluoronaphthyl)borate Dimethylanilinium 349 1396tetrakis(perfluorobiphenyl)borate [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄^(B)] 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe2H][(C6F3(C6F5)2)4B], and the types disclosed in U.S.Pat. No. 7,297,653.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes of this invention includeN,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph3C+][B(C6F5)4−],[Me3NH+][B(C6F5)4−];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl ismethyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

In a particularly preferred embodiment, the activator used incombination with any catalyst compound(s) described herein isN,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate.

In a preferred embodiment, any of the activators described herein may bemixed together before or after combination with the catalyst compound,preferably before being mixed with the catalyst compound.

In some embodiments, two NCA activators may be used in thepolymerization and the molar ratio of the first NCA activator to thesecond NCA activator can be any ratio. In some embodiments, the molarratio of the first NCA activator to the second NCA activator is 0.01:1to 10,000:1, preferably 0.1:1 to 1000:1, preferably 1:1 to 100:1.

Further, the typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is a 1:1 molar ratio. Alternate preferredranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1,alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this invention that the catalystcompounds can be combined with combinations of alumoxanes and NCA's (seefor example, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,453,410, EP 0 573120 B1, WO 94/07928, and WO 95/14044, which discuss the use of analumoxane in combination with an ionizing activator).

Optional Scavengers or Co-Activators

In addition to the activator compounds, scavengers or co-activators maybe used. Aluminum alkyl or organoaluminum compounds which may beutilized as scavengers or co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like. Other oxophilicspecies, such as diethyl zinc may be used.

Optional Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably, the support material is a porous support material,for example, talc, and inorganic oxides. Other support materials includezeolites, clays, organoclays, or any other organic or inorganic supportmaterial and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxides,such as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins, such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Preferredsupport materials include Al2O3, ZrO2, SiO2, and combinations thereof,more preferably SiO2, Al2O3, or SiO2/Al2O3.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m2/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m2/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 Gm.Most preferably the surface area of the support material is in the rangeof from about 100 to about 400 m2/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the support material useful in the invention is inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å. In some embodiments, the support materialis a high surface area, amorphous silica (surface area=300 m2/gm; porevolume of 1.65 cm3/gm). Preferred silicas are marketed under thetradenames of Davison 952 or Davison 955 by the Davison ChemicalDivision of W.R. Grace and Company. In other embodiments DAVISON 948 isused.

Polymer Products

The terms “polypropylene” and “propylene polymer” mean a polymercomprising at least 50 mol % propylene derived units. The term“polypropylene” is meant to encompass isotactic polypropylene (iPP)having at 10% or more isotactic pentads, highly isotactic polypropylenehaving 50% or more isotactic pentads, syndiotactic polypropylene (sPP)having at 10% or more syndiotactic pentads, homopolymer polypropylene(hPP, also called propylene homopolymer or homopolypropylene), andso-called random copolymer polypropylene (RCP, also called propylenerandom copolymer). Herein, an RCP is specifically defined to be acopolymer of propylene and 1 to 10 wt % of an olefin chosen fromethylene and C4 to C8 1-olefins. Preferably, the olefin comonomer in anRCP is ethylene or 1-butene, preferably ethylene. The term “EP Rubber”means a copolymer of ethylene and propylene, and optionally one or morediene monomer(s), where the ethylene content is from 35 to 85 mol %, thetotal diene content is 0 to 5 mol %, and the balance is propylene with aminimum propylene content of 15 mol %.

In any embodiment of the invention, the propylene polymer made in stageA is isotactic polypropylene or highly isotactic polypropylene,preferably homopolypropylene. In any embodiment of the invention, thepropylene polymer made in stage B is isotactic polypropylene or highlyisotactic polypropylene, preferably homopolypropylene. In an embodimentof the invention, the propylene polymer made in stage A is isotactichomopolypropylene or highly isotactic homopolypropylene. In anembodiment of the invention, the propylene polymer made in stage B isisotactic homopolypropylene or highly isotactic homopolypropylene. In apreferred embodiment, the propylene polymers made in stages A and B areboth isotactic polypropylene, but are different in at least one physicalcharacteristic, preferably the polymers differ in Mw, MFR, tacticity,comonomer content, Tm, Tc, Hf, or 1% Secant flexural modulus. In thiscontext differ means that the polymers differ by more than 1% relativeto each other, preferably by more than 5%, preferably by more than 10%,preferably by more than 15%, preferably by more than 20%, preferably bymore than 30%, preferably by more than 40%, preferably by more than 50%,preferably by more than 100%, preferably by more than 200%.

In any embodiment of the invention, the propylene polymer compositionsproduced herein may have a multimodal molecular weight distribution(Mw/Mn) of polymer species as determined by GPC-DRI. By multimodal ismeant that the GPC-DRI trace has more than one peak or inflection point.An inflection point is that point where the second derivative of thecurve changes in sign (e.g., from negative to positive or vice versa). Abimodal molecular weight distribution (Mw/Mn) is one having two peaks orinflection points.

In any embodiment of the invention, the propylene polymer (the Acomponent) advantageously has more than 15 and less than 200 regiodefects (defined as the sum of 2,1-erythro and 2,1-threo insertions, and3,1-isomerizations) per 10,000 propylene units, alternatively more than17 and less than 175 regio defects per 10,000 propylene units,alternatively more than 20 or 30 or 40, but less than 200 regio defects,alternatively less than 150 regio defects per 10,000 propylene units.The regio defects are determined using 13C NMR spectroscopy as describedbelow.

In any embodiment of the invention, the propylene polymer compositionproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), has more than 15 and less than200 regio defects (defined as the sum of 2,1-erythro and 2,1-threoinsertions, and 3,1-isomerizations) per 10,000 propylene units,alternatively more than 17 and less than 175 regio defects per 10,000propylene units, alternatively more than 20 or 30 or 40, but less than200 regio defects, alternatively less than 150 regio defects per 10,000propylene units. The regio defects are determined using 13C NMRspectroscopy as described below.

In any embodiment of the invention, the propylene polymer (A) componentcan have a melting point (Tm, DSC peak second melt) of at least 145° C.,or at least 150° C., or at least 152° C., or at least 155° C., or atleast 160° C., or at least 165° C., preferably from about 145° C. toabout 175° C., about 150° C. to about 170° C., about 152° C. to about165° C.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a melting point (Tm, DSCpeak second melt) of at least 145° C., or at least 150° C., or at least152° C., or at least 155° C., or at least 160° C., or at least 165° C.,preferably from about 145° C. to about 175° C., about 150° C. to about170° C., about 152° C. to about 165° C.

In any embodiment of the invention, the propylene polymer (A) componentcan have a 1% secant flexural modulus from a low of about 1100 MPa,about 1200 MPa, about 1250 MPa, about 1300 MPa, about 1400 MPa, or about1,500 MPa to a high of about 1,800 MPa, about 2,100 MPa, about 2,600MPa, or about 3,000 MPa, as measured according to ASTM D 790 (A, 1.0mm/min), preferably from about 1100 MPa to about 2,200 MPa, about 1200MPa to about 2,000 MPa, about 1400 MPa to about 2,000 MPa, or about 1500MPa or more. 1% Secant flexural modulus is determined by using an ISO37-Type 3 bar, with a crosshead speed of 1.0 mm/min and a support spanof 30.0 mm via an Instron machine according to ASTM D 790 (A, 1.0mm/min).

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), preferably have a 1% secantflexural modulus from about 1300 MPa to about 3,000 MPa, about 1500 MPato about 3000 MPa, about 1800 MPa to about 2,500 MPa, or about 1800 MPato about 2,000 MPa.

In any embodiment of the invention, the propylene polymer (A) componentcan have a melt flow rate (MFR, ASTM 1238, 230° C., 2.16 kg) from a lowof about 0.1 dg/min, about 0.2 dg/min, about 0.5 dg/min, about 1 dg/min,about 15 dg/min, about 30 dg/min, or about 45 dg/min to a high of about75 dg/min, about 100 dg/min, about 200 dg/min, or about 300 dg/min. Forexample, the polymer can have an MFR of about 0.5 dg/min to about 300dg/min, about 1 dg/min to about 300 dg/min, about 5 dg/min to about 150dg/min, or about 10 dg/min to about 100 dg/min, or about 20 dg/min toabout 60 dg/min.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have an MFR (ASTM 1238, 230°C., 2.16 kg) of from about 1 dg/min to about 300 dg/min, about 5 dg/minto about 150 dg/min, or about 10 dg/min to about 100 dg/min, or about 20dg/min to about 60 dg/min, preferably from about 50 to about 200 dg/min,preferably from about 55 to about 150 dg/min, preferably from about 60to about 100 dg/min.

In any embodiment of the invention, the propylene polymer (A) componentcan have an Mw (as measured by GPC-DRI) from 50,000 to 1,000,000 g/mol,alternately from 80,000 to 1,000,000 g/mol, alternately from 100,000 to800,000 g/mol, alternately from 200,000 to 600,000 g/mol, alternatelyfrom 300,000 to 550,000 g/mol, alternately from 330,000 g/mol to 500,000g/mol.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have an Mw (as measured byGPC-DRI) from 50,000 to 1,000,000 g/mol, alternately from 80,000 to1,000,000 g/mol, alternately from 100,000 to 800,000 g/mol, alternatelyfrom 200,000 to 600,000 g/mol, alternately from 300,000 to 550,000g/mol, alternately from 330,000 g/mol to 500,000 g/mol.

In any embodiment of the invention, the propylene polymer (A) componentcan have an Mw/Mn (as measured by GPC-DRI) of greater than 1 to 20,preferably 1.1 to 15, preferably 1.2 to 10, preferably 1.3 to 5,preferably 1.4 to 4.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have an Mw/Mn (as measured byGPC-DRI) of greater than 5 to 50, preferably 5.5 to 45, preferably 6 to40, preferably 6.5 to 35, preferably 7 to 30.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a total propylenecontent of at least 75 wt %, at least 80 wt %, at least 85 wt %, atleast 90 wt %, or at least 95 wt %, or 100 wt % based on the weight ofthe propylene polymer composition.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a total comonomercontent from about 1 wt % to about 35 wt %, about 2 wt % to about 30 wt%, about 3 wt % to about 25 wt %, or about 5 wt % to about 20 wt %,based on the total weight of the propylene polymer compositions, withthe balance being propylene.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a propylene meso diadscontent of 90% or more, 92% or more, about 94% or more, or about 96% ormore. Polypropylene microstructure is determined according to the 13CNMR procedure described below.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a melting point (Tm, DSCpeak second melt) from at least 100° C. to about 175° C., about 105° C.to about 170° C., about 110° C. to about 165° C., or about 115° C. toabout 155° C.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a crystallization point(Tc, DSC) of 115° C. or more, preferably from at least 100° C. to about150° C., about 105° C. to about 130° C., about 110° C. to about 125° C.,or about 115° C. to about 125° C.

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a CDBI of 50% or more(preferably 60% or more, alternately 70% or more, alternately 80% ormore, alternately 90% or more, alternately 95% or more).

In any embodiment of the invention, the propylene polymer compositionsproduced herein, particularly the composition produced after Stage A andStage B (the combined A&B components), can have a multimodal (such asbimodal) molecular weight distribution (Mw/Mn) distribution of polymerspecies.

In a preferred embodiment, the propylene polymer composition producedherein has:

a) at least 50 mol % propylene (preferably from 50 to 100 mol %,preferably from 60 to 97 mol %, preferably from 65 to 95 mol %,preferably from 70 to 90 mol %, preferably at least 90 mol %, from 50 to99 mol %) and optionally at least 1 mol % comonomer (preferably from 1to 50 mol %, preferably from 3 to 40 mol %, preferably from 5 to 35 mol%, preferably from 10 to 30 mol %) based upon the weight of thepropylene polymer composition;b) a 1% secant flexural modulus of at least 1500 MPa (preferably atleast 1600 MPa, preferably at least 1800 MPa);c) an Mw/Mn of at least 5, as determined GPC-DRI (preferably from 5 to40, preferably from 6 to 20, preferably from 7 to 15);d) a melt flow rate of 50 dg/min or more, as determined by ASTM D 1238,230° C., 2.16 kg (preferably 60 dg/min or more, preferably 75 dg/min ormore);e) a multimodal Mw/Mn, as determined by GPC-DRI;f) more than 15 and less than 200 regio defects (sum of 2,1-erythro and2,1-threo insertions and 3,1-isomerizations) per 10,000 propylene units,as determined by ¹³C NMR spectroscopy (preferably from 17 to 175 regiodefects per 10,000 propylene units, alternatively more than 20 or 30 or40, but less than 200 regio defects, alternatively less than 150 regiodefects per 10,000 propylene units); and, optionally,g) if comonomer is present, a CDBI of 50% or more (preferably 60% ormore, alternately 70% or more, alternately 80% or more, alternately 90%or more, alternately 95% or more).

In any embodiment described herein, propylene copolymer composition mayhave a melting point (Tm, DSC peak second melt) from at least 100° C. toabout 175° C., about 105° C. to about 170° C., about 110° C. to about165° C., or about 115° C. to about 155° C., and a crystallization point(Tc, DSC peak second melt) of 115° C. or more, preferably from at least100° C. to about 150° C., about 105° C. to about 130° C., about 110° C.to about 125° C., or about 115° C. to about 125° C.

In any embodiment described herein, the propylene homo- or co-polymerproduced by the process described herein has a Rabinowitch correctedshear viscosity (“RCSV”) ratio (1 sec-1 to 2000 sec-1) of Y or morewhere Y=38000X−1.559, and X is the melt flow rate in dg/min of thepropylene polymer, preferably Y=45000X−1.559, preferably Y=50524X−1.559.Shear viscosity is determined by capillary rheology on an ARC 2rheometer at 190° C. using a 1 mm die with a path length of 30 mmaccording to ASTM D3835. Rabinowitch correction is performed asdescribed at B. Rabinowitsch, Z. Physik. Chem., A 145, 1 (1929) usingsoftware program LAB KARS Advanced Rheology Software version 3.92available from Alpha Technologies Services, Akron, Ohio.

In a preferred embodiment, the propylene polymer composition producedherein has:

a) at least 50 mol % propylene (preferably from 50 to 100 mol %,preferably from 60 to 97 mol %, preferably from 65 to 95 mol %,preferably from 70 to 90 mol %, preferably at least 90 mol %, from 50 to99 mol %) and optionally at least 1 mol % comonomer (preferably from 1to 50 mol %, preferably from 3 to 40 mol %, preferably from 5 to 35 mol%, preferably from 10 to 30 mol %) based upon the weight of thepropylene polymer composition;b) a 1% secant flexural modulus of at least 1500 MPa (preferably atleast 1600 MPa, preferably at least 1800 MPa);c) an Mw/Mn of at least 5, as determined GPC-DRI (preferably from 5 to40, preferably from 6 to 20, preferably from 7 to 15);d) a melt flow rate of 50 dg/min or more, as determined by ASTM D 1238,230° C., 2.16 kg (preferably 60 dg/min or more, preferably 75 dg/min ormore);e) a multimodal Mw/Mn, as determined by GPC-DRI;f) more than 15 and less than 200 regio defects (sum of 2,1-erythro and2,1-threo insertions and 3,1-isomerizations) per 10,000 propylene units,as determined by ¹³C NMR spectroscopy (preferably from 17 to 175 regiodefects per 10,000 propylene units, alternatively more than 20 or 30 or40, but less than 200 regio defects, alternatively less than 150 regiodefects per 10,000 propylene units);g) if comonomer is present, a CDBI of 50% or more (preferably 60% ormore, alternately 70% or more, alternately 80% or more, alternately 90%or more, alternately 95% or more); andh) an RCSV ratio (1 sec⁻¹ to 2000 sec⁻¹) of Y or more whereY=38000X^(−1.559), and X is the melt flow rate in dg/min of thepropylene polymer (preferably Y=45000X^(−1.559), preferablyY=50524X^(−1.559))

In another embodiment, this invention relates to, an in-situ propylenepolymer comprising at least 50 mole % propylene, said in-situ propylenepolymer composition having a 1% secant flexural modulus of at least 1500MPa, an Mw/Mn of at least 5, a multimodal Mw/Mn as determined byGPC-DRI, a melt flow rate of 50 dg/min or more, and an RCSV ratio (1sec-1 to 2000 sec-1) of Y or more where Y=38000X−1.559, and X is themelt flow rate in dg/min of the propylene polymer, preferablyY=45000X−1.559, preferably Y=50524X−1.559.

In another embodiment, the propylene polymer composition produced aftertime period B has a 1% secant flexural modulus at least 150 MPa greaterthan the polymer produced after time period A (preferably at least 200MPa greater).

Impact Copolymer

A “polypropylene impact copolymer” (herein simply referred to as an“impact copolymer” (ICP)) is a blend typically comprising 60 to 95 wt %of (Component A plus or minus Component B) isotactic PP (typically witha Tm of 120° C. or more), and 5 to 40 wt % of (C) propylene polymer(often a copolymer) typically with a Tg of −30° C. or less, ethylenecopolymer typically with a Tg of −30° C. or less or an EP Rubber. Themorphology of an ICP is typically such that the matrix phase iscomprised primarily of component (A) while the dispersed phase iscomprised primarily of component (C) or is co-continuous. Typically, theICP comprises only two monomers: propylene and a single comonomer chosenfrom among ethylene and C4 to C8 alpha-olefins (preferably ethylene,butene, hexene or octene, preferably ethylene). Alternately, the ICPcomprises three monomers: propylene and two comonomers chosen from amongethylene and C4 to C8 alpha-olefins (preferably ethylene, butene, hexeneand octene). Preferably, the (A) component has a Tm of 120° C. or more(preferably 130° C. or more, preferably 140° C. or more, preferably 150°C. or more, preferably 160° C. or more). Preferably, the (C) componentis an amorphous polymer such as a propylene polymer or EP Rubber.Preferably, the (C) component has a Tg of −30° C. or less (preferably−40° C. or less, preferably −50° C. or less).

In an embodiment of the invention, the (C) component has a heat offusion (Hf) of 90° C. or less (as determined by DSC). Preferably the (C)component has an Hf of 70° C. or less, preferably 50° C. or less,preferably 35° C. or less.

In an embodiment of the invention, the propylene polymer made in stage Ahas a propylene tacticity index of greater than 4 (preferably 4-6), thepolypropylene made in stage B has a propylene tacticity index of greaterthan 4 (preferably 4-6), and the final impact copolymer (the combinationof A, B and C) has an mm triad tacticity index of 75% or more preferably80% or more, preferably 85% or more. In an embodiment of the invention,the propylene polymer made in stage A is isotactic polypropylene orhighly isotactic polypropylene, preferably homopolypropylene. In anembodiment of the invention, the propylene polymer made in stage B isisotactic polypropylene or highly isotactic polypropylene, preferablyhomopolypropylene. In an embodiment of the invention, the propylenepolymer made in stage C is atactic.

Preferably the ICP produced from Stages A, B and C is heterophasic. Theterm “hetero-phase” refers to the presence of two or more morphologicalphases in a blend of two or more polymers, where each phase comprises adifferent ratio of the polymers as a result of partial or completeimmiscibility (i.e., thermodynamic incompatibility). A common example isa morphology consisting of a “matrix” (continuous) phase and at leastone “dispersed” (discontinuous) phase. The dispersed phase takes theform of discrete domains (particles) distributed within the matrix (orwithin other phase domains, if there are more than two phases). Anotherexample is a co-continuous morphology, where two phases are observed butit is unclear which is the continuous phase and which is thediscontinuous phase. The presence of multiple phases is determined usingmicroscopy techniques, e.g., optical microscopy, scanning electronmicroscopy (SEM), or atomic force microscopy (AFM); or by the presenceof two glass transition peaks in a dynamic mechanical analysis (DMA)experiment; in the event of disagreement among these methods, the AFMdetermination shall be used.

In a preferred embodiment, the impact copolymer has a matrix phasecomprising primarily a propylene polymer composition having a meltingpoint (Tm) of 100° C. or more, an MWD of 5 of more and a multimodal MWD,and the dispersed phase comprises primarily a polyolefin having a glasstransition temperature (Tg) of −20° C. or less. Preferably, the matrixphase comprises primarily homopolymer polypropylene (hPP) and/or randomcopolymer polypropylene (RCP) with relatively low comonomer content(less than 5 wt %), and has a melting point of 110° C. or more(preferably 120° C. or more, preferably 130° C. or more, preferably 140°C. or more, preferably 150° C. or more, preferably 160° C. or more).Preferably, the dispersed phase comprises primarily one or more ethyleneor propylene copolymer(s) with relatively high comonomer content (atleast 5 wt %, preferably at least 10 wt %); and has a Tg of −30° C. orless (preferably −40° C. or less, preferably −50° C. or less).

An “in-situ ICP” is a specific type of ICP which is a reactor blend ofthe (A&B) and (C) components of an ICP, meaning (A), (B) and (C) weremade in separate reactors (or reactions zones) physically connected inseries, with the effect that an intimately mixed final product isobtained in the product exiting the final reactor (or reaction zone).Typically, the components are produced in a sequential polymerizationprocess, wherein (A) is produced in a first reactor is transferred to asecond reactor where (B) is produced in a second reactor, and theproduct is transferred to a third reactor where (C) is produced andincorporated as domains into the (A&B) matrix. There may also be a minoramount of a third component (D), produced as a byproduct during thisprocess, comprising primarily the non-propylene comonomer (e.g., (D)will be an ethylene polymer if ethylene is used as the comonomer). Inthe literature, especially in the patent literature, an in-situ ICP issometimes identified as “reactor-blend ICP” or a “block copolymer”,although the latter term is not strictly accurate since there is at bestonly a very small fraction of molecules that are (A)-(C) copolymers. Ina preferred embodiment of the invention, the polymer compositionproduced herein is an in-situ-ICP.

An “ex-situ ICP” is a specific type of ICP which is a physical blend of(A&B) and (C), meaning (A&B) and (C) were synthesized independently andthen subsequently blended typically using a melt-mixing process, such asan extruder. An ex-situ ICP is distinguished by the fact that (A&B) and(C) are collected in solid form after exiting their respective synthesisprocesses, and then combined; whereas for an in-situ ICP, (A) (B) and(C) are combined within a common synthesis process and only the blend iscollected in solid form.

In one or more embodiments, the impact copolymer (the combination of A,B and C components) advantageously has more than 15 and less than 200regio defects (defined as the sum of 2,1-erythro and 2,1-threoinsertions, and 3,1-isomerizations) per 10,000 propylene units,alternatively more than 17 and less than 175 regio defects per 10,000propylene units, alternatively more than 20 or 30 or 40, but less than200 regio defects, alternatively less than 150 regio defects per 10,000propylene units. The regio defects are determined using 13C NMRspectroscopy as described below.

The impact polymers produced after stage C, typically have aheterophasic morphology such that the matrix phase is primarilypropylene polymer having a Tm of 120° C. or more and the dispersed phaseis primarily an ethylene copolymer (such as EP Rubber) or propylenepolymer typically having a Tg of −30° C. or less.

The impact copolymers produced herein preferably have a total propylenecontent of at least 75 wt %, at least 80 wt %, at least 85 wt %, atleast 90 wt %, or at least 95 wt %, or 100 wt % based on the weight ofthe propylene polymer composition.

The impact copolymers produced herein preferably have a total comonomercontent from about 1 wt % to about 35 wt %, about 2 wt % to about 30 wt%, about 3 wt % to about 25 wt %, or about 5 wt % to about 20 wt %,based on the total weight of the propylene polymer compositions, withthe balance being propylene.

Preferred impact copolymers comprise isotactic polypropylene (typicallyfrom Stage A and B) and ethylene copolymer (typically from Stage C) andtypically have an ethylene copolymer (preferably ethylene propylenecopolymer, preferably EP Rubber) content from a low of about 5 wt %,about 8 wt %, about 10 wt %, or about 15 wt % to a high of about 25 wt%, about 30 wt %, about 38 wt %, or about 42 wt %. For example, theimpact polymer can have an ethylene copolymer content of about 5 wt % toabout 40 wt %, about 6 wt % to about 35 wt %, about 7 wt % to about 30wt %, or about 8 wt % to about 30 wt %.

In preferred impact copolymers comprising isotactic polypropylene (fromstage A and B) and ethylene copolymer (from Stage C), the impactcopolymer can have a propylene content of the ethylene copolymercomponent from a low of about 25 wt %, about 37 wt %, or about 46 wt %to a high of about 73 wt %, about 77 wt %, or about 80 wt %, based onthe weight of the ethylene copolymer. For example, the impact copolymercan have a propylene content of the ethylene copolymer component fromabout 25 wt % to about 80 wt %, about 10 wt % to about 75 wt %, about 35wt % to about 70 wt %, or at least 40 wt % to about 80 wt %, based onthe weight of the ethylene copolymer.

The impact copolymers produced herein preferably have a heat of fusion(Hf, DSC second heat) of 60 J/g or more, 70 J/g or more, 80 J/g or more,90 J/g or more, about 95 J/g or more, or about 100 J/g or more.

The impact polymers produced herein preferably have a 1% secant flexuralmodulus from about 300 MPa to about 3,000 MPa, about 500 MPa to about2,500 MPa, about 700 MPa to about 2,000 MPa, or about 900 MPa to about2,000 MPa, as measured according to ASTM D 790 (A, 1.0 mm/min).

The impact polymers, produced herein preferably have an Mw (as measuredby GPC-DRI) from 50,000 to 1,000,000 g/mol, alternately from 80,000 to1,000,000 g/mol, alternately 100,000 to 800,000 g/mol, alternately200,000 to 600,000 g/mol, alternately from 300,000 to 550,000 g/mol,alternately from 330,000 g/mol to 500,000 g/mol.

¹³C-NMR Spectroscopy on Polyolefins

Polypropylene microstructure is determined by 13C-NMR spectroscopy,including the concentration of isotactic and syndiotactic diads ([m] and[r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Thedesignation “m” or “r” describes the stereochemistry of pairs ofcontiguous propylene groups, “m” referring to meso and “r” to racemic.Samples are dissolved in d2-1,1,2,2-tetrachloroethane at 120° C., andspectra are acquired with a 10-mm broadband probe recorded at 120° C.using a 400 MHz (or higher) NMR spectrometer (such as Varian Inova 700or Unity Plus 400, in event of conflict the 700 shall be used). Polymerresonance peaks are referenced to mmmm=21.83 ppm. Calculations involvedin the characterization of polymers by NMR are described by F. A. Boveyin Polymer Conformation and Configuration (Academic Press, New York1969) and J. Randall in Polymer Sequence Determination, 13C-NMR Method(Academic Press, New York, 1977).

The “propylene tacticity index”, expressed herein as [m/r], iscalculated as defined in H. N. Cheng, Macromolecules, 17, p. 1950(1984). When [m/r] is 0 to less than 1.0, the polymer is generallydescribed as syndiotactic, when [m/r] is 1.0 the polymer is atactic, andwhen [m/r] is greater than 1.0 the polymer is generally described asisotactic.

The “mm triad tacticity index” of a polymer is a measure of the relativeisotacticity of a sequence of three adjacent propylene units connectedin a head-to-tail configuration. More specifically, in the presentinvention, the mm triad tacticity index (also referred to as the “mmFraction”) of a polypropylene homopolymer or copolymer is expressed asthe ratio of the number of units of meso tacticity to all of thepropylene triads in the copolymer:

${{mm}\mspace{14mu}{Fraction}} = \frac{{PPP}({mm})}{{{PPP}({mm})} + {{PPP}({mr})} + {{PPP}({rr})}}$where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from themethyl groups of the second units in the possible triad configurationsfor three head-to-tail propylene units, shown below in Fischerprojection diagrams:

The calculation of the mm Fraction of a propylene polymer is describedin U.S. Pat. No. 5,504,172 (homopolymer: column 25, line 49 to column27, line 26; copolymer: column 28, line 38 to column 29, line 67). Forfurther information on how the mm triad tacticity can be determined froma ¹³C-NMR spectrum, see 1) J. A. Ewen, Catalytic Polymerization ofOlefins: Proceedings of the International Symposium on Future Aspects ofOlefin Polymerization, T. Keii and K. Soga, Eds. (Elsevier, 1986), pp.271-292; and 2) U.S. Patent Application US2004/054086 (paragraphs [0043]to [0054]).

An “isotactic” polymer has at least 10% isotactic pentads, a “highlyisotactic” polymer has at least 50% isotactic pentads, and a“syndiotactic” polymer has at least 10% syndiotactic pentads, accordingto analysis by 13C-NMR. Preferably isotactic polymers have at least 20%(preferably at least 30%, preferably at least 40%) isotactic pentads. Apolyolefin is “atactic,” also referred to as amorphous” if it has lessthan 10% isotactic pentads and syndiotactic pentads.

Regio Defect Concentrations by ¹³C NMR

13Carbon NMR spectroscopy is used to measure stereo and regio defectconcentrations in the polypropylene. 13-Carbon NMR spectra are acquiredwith a 10-mm broadband probe on a Varian Inova 700 or UnityPlus 400spectrometer (in event of conflict the 700 shall be used). The sampleswere prepared in 1,1,2,2-tetrachloroethane-d2 (TCE). Sample preparation(polymer dissolution) was performed at 120° C. In order to optimizechemical shift resolution, the samples were prepared without chromiumacetylacetonate relaxation agent. Signal-to-noise was enhanced byacquiring the spectra with nuclear Overhauser enhancement for 10 secondsbefore the acquisition pulse, and 3.2 second acquisition period, for anaggregate pulse repetition delay of 14 seconds. Free induction decays of3400-4400 coadded transients were acquired at a temperature of 120° C.After Fourier transformation (256 K points and 0.3 Hz exponential linebroadening), the spectrum is referenced by setting the dominant mmmmmeso methyl resonance to 21.83 ppm.

Chemical shift assignments for the stereo defects (given as stereopentads) can be found in the literature [L. Resconi, L. Cavallo, A.Fait, and F. Piemontesi, Chem. Rev. 2000, 100, pp. 1253-1345]. Thestereo pentads (e.g. mmmm, mmmr, mrrm, etc.) can be summed appropriatelyto give a stereo triad distribution (m, mr, and rr), and the molepercentage of stereo diads (m and r). Three types of regio defects werequantified: 2,1-erythro, 2,1-threo, and 3,1-isomerization. Thestructures and peak assignments for these are also given in thereference by Resconi. The concentrations for all defects are quoted interms of defects per 10,000 monomer units.

The regio defects each give rise to multiple peaks in the carbon NMRspectrum, and these are all integrated and averaged (to the extent thatthey are resolved from other peaks in the spectrum), to improve themeasurement accuracy. The chemical shift offsets of the resolvableresonances used in the analysis are tabulated below. The precise peakpositions may shift as a function of NMR solvent choice.

regio defect Chemical shift range (ppm) 2,1-erythro 42.3, 38.6, 36.0,35.9, 31.5, 30.6, 17.6, 17.2 2,1-threo 43.4, 38.9, 35.6, 34.7, 32.5,31.2, 15.4, 15.0 3,1 insertion 37.6, 30.9, 27.7

The average integral for each defect is divided by the integral for oneof the main propylene signals (CH3, CH, CH2), and multiplied by 10,000to determine the defect concentration per 10,000 monomer units.

Ethylene content in ethylene copolymers is determined by ASTM D 5017-96,except that the minimum signal-to-noise should be 10,000:1. Propylenecontent in propylene copolymers is determined by following the approachof Method 1 in Di Martino and Kelchermans, J. Appl. Polym. Sci., 56, p.1781 (1995), and using peak assignments from Zhang, Polymer, 45, p. 2651(2004) for higher olefin comonomers.

Composition Distribution Breadth index (CDBI) is a measure of thecomposition distribution of monomer within the polymer chains. It ismeasured as described in WO 93/03093, with the modification that anyfractions having a weight-average molecular weight (Mw) below 20,000g/mol are ignored in the calculation.

In another embodiment, this invention relates to:

1. A process to polymerize propylene comprising:

1) contacting propylene, optionally with a comonomer, with a catalystsystem comprising an activator and a catalyst compound represented bythe formula:

where:M is a group 4 metal (preferably Hf or Zr);T is a bridging group (preferably dialkylsilyl, such as dimethylsilyl);X is an anionic leaving group (such as a halogen or hydrocarbyl, such asCl or Me);each R³, R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², and R¹³ is independently, halogenatom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, substituted silylcarbyl,germylcarbyl, substituted germylcarbyl substituents or a —NR′₂, —SR′,—OR′, —OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogen atom, aC₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;each R² and R⁸ is independently, a hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;R⁴ and R¹⁰ are, independently, a substituted or unsubstituted aryl group(preferably substituted or unsubstituted phenyl group);2) polymerizing the propylene and optional comonomer for a time period,A;3) adding hydrogen or other chain termination agent and optionalcomonomer to the polymerization after time period A;4) polymerizing in the presence of at least 1 mmol hydrogen per mol ofpropylene for a time period, B, where time period A is at least as longas time period B and the hydrogen concentration during time period B isat least three times greater than the hydrogen concentration in timeperiod A (preferably the time period A is at least 1.5 times longer thantime period B); and5) obtaining a propylene polymer composition having:

-   -   a) at least 50 mol % propylene;    -   b) a 1% secant flexural modulus of at least 1500 MPa;    -   c) an Mw/Mn of at least 5;    -   d) a melt flow rate of 50 dg/min or more (230° C., 2.16 kg);    -   e) a multimodal Mw/Mn; and    -   f) more than 15 and less than 200 regio defects (sum of        2,1-erythro and 2,1-threo insertions and 3,1-isomerizations) per        10,000 propylene units.        2. The process of any of paragraphs 1 through 4, wherein the        propylene polymer composition contains at least 70 mol %        propylene, alternately at least 80 mol % propylene, alternately        about 100% propylene.        3. The process of any of paragraphs 1 through 2, wherein the        melt flow rate of the propylene polymer composition is from        about 50 to about 200 dg/min; and wherein the propylene polymer        composition produced is isotactic and/or has an mm triad        tacticity index of about 75% or greater.        4. The process of any of paragraphs 1 through 3, wherein R² and        R⁸ are, independently, methyl, ethyl, propyl, butyl, pentyl,        hexyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers of        mixtures thereof, preferably R² and R⁸ are cyclopropyl or        methyl; and R⁴ and R¹⁰ are, independently, an aryl group,        substituted with another group at the ortho position, preferably        the phenyl groups are substituted at the ortho position with        aryl groups or by linker groups, wherein the linker groups are        an alkyl, vinyl, phenyl, alkynyl, silyl, germyl, amine,        ammonium, phosphine, phosphonium, ether, thioether, borane,        borate, alane or aluminate groups, preferably R⁴ and R¹⁰ are        both biphenyl groups.        5. The process of any of paragraphs 1 through 4, wherein the        polymerizations of time period A and time period B occur in the        same reaction zone or different reaction zones.        6. The process of any of paragraphs 1 through 5, wherein the        activator comprises an alumoxane and or a non-coordinating anion        activator.        7. The process of any of paragraphs 1 through 6, wherein the        catalyst is supported, preferably on silica.        8. The process of any of paragraphs 1 through 7, wherein the        process is a slurry process or a homogeneous process or a gas        phase process.        9. The process of any of paragraphs 1 through 8, wherein R² is a        hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted        halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl,        or substituted germylcarbyl substituent;        R⁴ is an aryl group substituted at the ortho position with        another aryl group or by a linker group, wherein the linker        group is an alkyl, vinyl, phenyl, alkynyl, silyl, germyl, amine,        ammonium, phosphine, phosphonium, ether, thioether, borane,        borate, alane or aluminate groups;        R⁸ is a halogen atom, a C₁-C₁₀ alkyl group which may be        halogenated, a C₆-C₁₀ aryl group which may be halogenated, a        C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀        alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′,        —OR′, —OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogen        atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group; and        R¹⁰ is phenyl group substituted at the 3′ and 5′ positions,        independently, with a C₁-C₁₀ alkyl group.        10. A process to produce a propylene impact copolymer        comprising: performing steps 1 to 4 in any of paragraphs 1 to 9        and thereafter        5) adding comonomer comprising ethylene and/or a C₄-C₄₀ olefin        monomer to the polymerization after time period B for a time        period, C; and        6) obtaining a propylene polymer composition having:    -   a) at least 50 mol % propylene and at least 1 mol % comonomer;    -   b) a 1% secant flexural modulus of at least 1500 MPa;    -   c) an Mw/Mn of at least 5;    -   d) a melt flow rate of 50 dg/min or more (230° C., 2.16 kg);    -   e) a multimodal Mw/Mn;    -   f) more than 15 and less than 200 regio defects (sum of        2,1-erythro and 2,1-threo insertions and 3,1-isomerizations) per        10,000 propylene units; and    -   g) a CDBI of 50% or more.        11. The process of paragraph 10, where the comonomer added to        the polymerization after time period A is selected from ethylene        and a C₄-C₄₀ olefin monomers.        12. The process of any of the above paragraphs, where the        polymer composition obtained comprises at least 50 mole %        propylene and at least 1 mol % comonomer, and has a CDBI of 50%        or more, a 1% secant flexural modulus of at least 1500 MPa, an        Mw/Mn of at least 5, and a melt flow rate of 50 dg/min or more;        and optionally has more than 15 and less than 100 regio defects        per 10,000 propylene units.        13. The process of any of the above paragraphs, where the        polymer composition obtained has a multimodal Mw/Mn as        determined by GPC-DRI.        14. The process of any of the above paragraphs 1 to 11, where        the polymer composition obtained comprises at least 50 mole %        propylene, said propylene polymer composition having a 1% secant        flexural modulus of at least 1500 MPa, an Mw/Mn of at least 5, a        multimodal Mw/Mn as determined by GPC-DRI, a melt flow rate of        50 dg/min or more, and an RCSV ratio (1 sec⁻¹ to 2000 sec⁻¹) of        Y or more, where Y=38000X^(−1.559), and X is the melt flow rate        in dg/min of the propylene polymer.        15. The process of any of the above paragraphs 1 to 13, wherein        the propylene polymer composition has an RCSV ratio (1 sec⁻¹ to        2000 sec⁻¹) of Y or more, where Y=38000X^(−1.559), and X is the        melt flow rate in dg/min of the propylene polymer.        16. A propylene polymer having a melt flow ratio or 50 dg/min or        more and an RCSV ratio (1 sec⁻¹ to 2000 sec⁻¹) of Y or more,        where Y=38000X^(−1.559), and X is the melt flow rate in dg/min        of the propylene polymer.        17. An injection molded article comprising the in-situ propylene        polymer of paragraph 16, or produced by the process of any of        paragraphs 1-15, where the in-situ polymer has a 1% secant        flexural modulus of at least 1600 MPa.        18. An injection molded article comprising the propylene polymer        composition produced by the process of any of paragraphs 1-15,        where the propylene polymer composition has a 1% secant flexural        modulus at least 150 MPa greater than the polymer produced after        time period A (preferably at least 200 MPa greater).

EXPERIMENTAL Synthesis Dimethylsilylbis(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)zirconiumdichloride

Indene Synthesis

4-Bromo-2,3-dihydro-1H-inden-1-one (2)

3-(2-Bromophenyl)propanoic acid (1) (550 g, 2.4 mol, 1 equiv) wasdissolved in 1,2-dichloroethane (5.5 L). Thionyl chloride (437.8 mL, 6mol, 2.5 equiv) was added to the solution and the mixture was refluxedfor 24 hours. The reaction was cooled to room temperature andconcentrated under reduced pressure. The residue was dissolved inmethylene chloride (1 L) and added dropwise to a mechanically stirredsuspension of anhydrous aluminum chloride (526.9 g, 3.96 mol, 1.65equiv) in dichloromethane (1 L) while keeping the reaction temperaturebelow 27° C. The reaction was stirred at room temperature for threehours before being quenched into a five gallon bucket which washalf-full of ice. The resulting mixture was extracted withdichloromethane (3×3 L). The combined organic layers were washedsequentially with saturated brine (2 L) and saturated sodium bicarbonate(2 L). The organic layer was dried over sodium sulfate, and concentratedunder reduced pressure. The resulting solid was dried overnight in avacuum oven at 30° C. to give compound 2 (435 g, 86% yield) as anoff-white solid.

4-Bromo-2,3-dihydro-1H-inden-1-ol (3)

A solution of compound 2 (435 g, 2.06 mol, 1 equiv) in ethanol (5 L) wastreated with sodium borohydride (101.6 g, 2.68 mol, 1.3 equiv) andstirred overnight at room temperature. The reaction was concentratedunder reduced pressure and the residue partitioned between 4 L ofdichloromethane and 4 L of 10% aqueous hydrochloric acid. The layerswere separated and the aqueous layer was extracted with dichloromethane(3×1 L). The combined organic layers were washed with saturated brine (2L), dried over sodium sulfate and concentrated under reduced pressure.The resulting solid was dried overnight in a vacuum oven at 30° C. togive compound 3 (422 g, 96% yield) as an off-white solid.

4-Bromo-1H-indene (4)

Compound 3 (150 g, 704 mmol, 1 equiv) was suspended in a mixture ofconcentrated sulfuric acid (250 mL) and water (1.25 L). The mixture wasrefluxed overnight. The reaction was cooled and extracted with 1.5 L ofdichloromethane. The organic layer was washed with saturated sodiumbicarbonate (1.5 L), dried over sodium sulfate, and concentrated underreduced pressure. The residue was purified over silica gel (800 g),eluting with heptanes to give compound 4 (95 g, 69% yield) as a lightyellow oil.

4-(3,5-Di-tert-butylphenyl)-1H-indene (5)

Mixture of compound 4 (60 g, 308 mmol, 1 equiv),2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (126g, 400 mmol, 1.3 equiv), powdered potassium carbonate (128 g, 924 mmol,3 equiv) and bis(triphenylphosphine)palladium(II)dichloride (25.3 g, 31mmol, 0.1 equiv), 1,4-dioxane (300 mL) and water (150 mL) was heatedovernight at 80° C. The reaction was poured into 700 mL of water andextracted with ethyl acetate (3×500 mL). The combined organic layerswere washed with saturated brine (1 L), dried over sodium sulfate, andconcentrated under reduced pressure. The resulting residue was purifiedover silica gel (1 Kg) eluting with heptanes to give compound 5 (59 g,63% yield) as a light yellow oil.

2-Bromo-4-(3,5-di-tert-butylphenyl)-1H-indene (6)

A cold solution (5° C.) of compound 5 (49 g, 161 mmol, 1 equiv),dimethyl sulfoxide (500 mL) and water (5 mL) was treated in one portionwith N-bromosuccinimide (43 g, 241 mmol, 1.5 equiv). The bath wasremoved and the reaction allowed to stir at room temperature overnight.The reaction was poured into water (1 L) and the mixture extracted withethyl acetate (2×500 mL). The combined organic layers were washed withsaturated brine (1 L), dried over sodium sulfate and concentrated underreduced pressure. The resulting residue was dissolved in toluene (500mL) and p-toluenesulfonic acid (6.2 g, 32.6 mmol, 0.2 equiv) was added.The mixture was refluxed for 20 hours while removing water with aDean-Stark trap. The reaction was cooled to room temperature andconcentrated under reduced pressure. The resulting residue was purifiedover silica gel (1 Kg) eluting with heptanes to give compound 6 (41 g,66% yield) as a white solid.

2-Cyclopropyl-4-(3,5-di-tert-butylphenyl)-1H-indene (7)

A solution of compound 6 (16.1 g, 42.0 mmol, 1 equiv) and anhydroustoluene (200 mL) was treated with[1,1′-bis(diphenylphos-phino)ferrocene]dichlopalladium(II) DCM adduct(3.43 g, 4.2 mmol, 0.1 equiv). After stirring for 10 minutes, 0.5 Mcyclopropylmagnesium bromide in tetrahydrofuran (420 mL, 210 mmol, 5equiv) was added dropwise. The reaction was heated at 60° C. overnight.The reaction was cooled with an ice bath, acidified with 1N HCl to pH 3and extracted with ethyl acetate (3×500 mL). The combined organic layerswere washed with saturated brine (800 mL), dried over sodium sulfate,and concentrated under reduced pressure. The residue was purified on anAnaLogix (65-200 g) column with dry-loading, eluting with heptanes togive compound 7 (7.0 g, 48% yield) as a white solid.

Lithium {1-[2-cyclopropyl-4-(3,5-di-tert-butylphenyl)indenide]}

A solution of 2-cyclopropyl-7-(3,5-di-tert-butylphenyl)-indene (5.93 g,17.21 mmol) in diethyl ether (40 mL) was precooled at −35° C. for 30min. nBuLi (2.5 M, 7 mL, 17.5 mmol) was added. The solution was stirredat room temperature for 16 h. All volatiles were evaporated. The residuewas washed with pentane (10 mL×4, 40 mL×1) and dried under vacuum togive the crude product (4.68 g).

Chloro(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilane

A solution of lithium{1-[2-cyclopropyl-4-(3,5-di-tert-butylphenyl)indenide]}(2.38 g, 6.791mmol) in diethyl ether (30 mL) was precooled at −35° C. for 10 min.Me2SiCl2 (12.9 g, 99.95 mmol) was added and the white slurry was stirredat room temperature for 28 h. All volatiles were evaporated. The residuewas extracted with pentane (40 mL). The pentane filtrate was evaporatedto dryness under vacuum to givechloro(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilaneas a white sticky solid (1.68 g).

(2-Cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilyltrifluoromethanesulfonate

A solution ofchloro(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilane(1.64 g, 3.752 mmol) in toluene (10 mL) was added to stirring mixture ofsilver trifluoromethanesulfonate (1 g, 3.892 mmol) in toluene (10 mL).The slurry was stirred at room temperature for 3 h. Toluene was removedunder vacuum and the residue was extracted with pentane (40 mL). Thepentane filtrate was concentrated under vacuum to give crude(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilyltrifluoromethanesulfonate (1.93 g).

Bis(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilane

A precooled solution of lithium{1-[2-cyclopropyl-4-(3,5-di-tert-butylphenyl)indenide]}(1.26 g, 3.595mmol) in diethyl ether (20 mL) was added to a precooled solution (−35°C. for 30 min) of(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)dimethylsilyltrifluoromethanesulfonate (1.93 g, 3.504 mmol) in diethyl ether (10 mL).The mixture was stirred at room temperature for 23 h. All volatiles wereremoved under vacuum. The residue was extracted with pentane (40 mL).The pentane filtrate was evaporated to dryness to give the crude product(2.6 g).

Dilithium dimethylsilylbis{1-[2-cyclopropyl-4-(3,5-di-tert-butylphenyl)indenide]}

Then the above crude product (2.54 g, 3.408 mmol) was dissolved indiethyl ether (25 mL) and precooled at −20° C. for 1 h. nBuLi (2.5 M,2.8 mL, 7 mmol) was added. The solution was stirred at room temperaturefor 22 h. All volatiles were removed under vacuum. The residue waswashed with pentane (5 mL×3) and dried under vacuum to give thedilithium compound as an Et2O (0.88 eq) adduct (2.66 g).

Dimethylsilylbis(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)zirconiumdichloride

A precooled solution of {dilithium dimethylsilylbis{1-[2-cyclopropyl-4-(3,5-di-tert-butylphenyl)indenide]}}[Et2O] 0.88(2.64 g, 3.211 mmol) in Et2O (15 mL) was added to precooled of ZrCl4(0.75 g, 3.218 mmol) in Et2O (20 mL). The slurry was stirred at roomtemperature for 20 h. The mixture was evaporated to dryness. The residuewas extracted with pentane (15 mL once, 5 mL once) (Fraction 1). Theresidue was then extracted with toluene (15 mL) (Fraction 2).

Fraction 1: The pentane filtrate was concentrated to dryness undervacuum to give the crude metallocene. Crystallization of the crudeproduct in pentane (20 mL) at −15° C. affords the metallocene with arac/meso-ratio of 7:1 (0.79 g, 27%). Further fractional crystallizationseparation yields rac-dimethylsilylbis(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)zirconiumdichloride as a yellow solid (0.15 g, 5.2%, rac meso ratio of greaterthan 20:1, hereinafter referred to as Catalyst A). (This fraction wasused for synthesis of supported catalyst).

Fraction 2: Toluene filtrate was concentrated to dryness to give 0.74 g(25%) of metallocenes with a rac/mese ratio of 1:28. Further washing 0.5g of this material with pentane affords 0.4 g of metallocene with arac/meso ratio of 1:56. ¹H NMR (400 MHz, C6D6, 23° C.): rac: δ 7.95 (m,4H), 7.62 (m, 2H), 7.49 (m, 4H), 6.98 (s, 2H), 6.90 (m, 2H), 1.84 (m,2H), 1.42 (s, 36H), 0.99 (s, 6H, SiMe2), 0.86 (m, 2H), 0.66 (m, 2H),0.50 (m, 2H), 0.13 (m, 2H). meso: 7.92 (m, 4H), 7.61 (m, 2H), 7.59-7.27(m, 4H), 6.86-6.82 (m, 4H), 1.91 (m, 2H), 1.44 (s, 36H), 1.27 (m, 2H),1.09 (s, 3H, SiMe), 0.91 (s, 3H, SiMe), 0.68 (m, 2H), 0.61 (m, 2H), 0.13(m, 2H).

Supported rac-Dimethylsilylbis(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)zirconiumdichloride (Catalyst-2)

In a 20 mL vial Catalyst A (rac-dimethylsilylbis(2-cyclopropyl-4-(3,5-di-tert-butylphenyl)-indenyl)zirconiumdichloride) (25.2 mg, 0.0278 mmol) was stirred alongside MAO (30% byweight in toluene, 0.2345 g of solution) along with another 2 mL oftoluene for 1 h. In a small celstir Davison 948 Silica (calcined at 130°C.) pretreated with MAO (SMAO) (0.6954 g) was slurried in 20 mL oftoluene. The celstir was chilled for 1 min in the freezer (−35° C.)before the catalyst solution was added to the slurry. The slurry wasstirred for 1 h while spending 1 min of every 10 min in the freezer. Theslurry was then heated to 40° C. and stirred for 2 h. The slurry wasfiltered using a fine glass frit, and then reslurried in 20 mL oftoluene and stirred for an additional 30 min at 60° C. The slurry wasfiltered again, and then reslurried in 20 mL of toluene and stirred foran additional 30 min at 60° C. The slurry was filtered, and thenreslurried in 20 mL of toluene and stirred for an additional 30 min at60° C. and then filtered for the final time. The celstir was washed outwith 20 mL of toluene and the solid was dried under vacuum. Collected0.619 g of pink solid. The SMAO is typically prepared as follows: 130°C. Calcined Davison 948 Silica (20.8606 g, calcined at 130° C.) wasslurried in 121 mL of toluene and chilled in the freezer (approx. −35°C.). MAO (50.5542 g of a 30% wt solution in toluene) was added slowly in3 parts with the silica slurry returned to the freezer for a few minutes(approx. 2 minutes) between additions. The slurry was stirred at roomtemperature for 2 h, filtered with a glass frit filter, reslurried in 80mL of toluene for 15 min at room temperature, and then filtered again.The solid was reslurried in 80 mL of toluene at 80° C. for 30 min andthen filtered. The solid was reslurried in 80 mL of toluene at 80° C.for 30 min and then filtered a final time. The celstir and solid werewashed out with 40 mL of toluene. The solid was then washed with pentaneand dried under vacuum for 24 h. Collected 28.9406 g of a free flowingwhite powder.

Dimethylsilyl(4-o-biphenyl-2-cyclopropyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)zirconiumdichloride

Indene Synthesis:

4-([1,1′-Biphenyl]-2-yl)-1H-indene (8): A mixture of compound 4 (40 g,205 mmol, 1 equiv), (biphenyl-2-yl)boronic acid (81.2 g, 410 mmol, 2equiv), powdered potassium carbonate (85 g, 615 mmol, 3 equiv), andbis(triphenylphosphine)palladium(II)dichloride (7.2 g, 10.3 mmol, 0.05equiv), 1,4-dioxane (300 mL) and water (150 mL) was heated overnight at80° C. The reaction was poured into 500 mL of water and extracted withethyl acetate (3×400 mL). The combined organic layers were washed withsaturated brine (300 mL), dried over sodium sulfate, and concentratedunder reduced pressure. The resulting residue was purified over silicagel (400 g) eluting with heptanes to give compound (8) (50 g, 91% yield)as a light-yellow oil that slowly turned to an off-white solid onstanding.

4-([1,1′-Biphenyl]-2-yl)-2-bromo-1H-indene (9)

A cold solution (5° C.) of compound 8 (40 g, 149 mmol, 1 equiv),dimethyl sulfoxide (400 mL) and water (5 mL) was treated in one portionwith N-bromosuccinimide (39.8 g, 224 mmol, 1.5 equiv). The bath wasremoved and the reaction allowed to stir at room temperature overnight.The reaction was poured into water (1 L) and extracted with ethylacetate (2×500 mL). The combined organic layers were washed withsaturated brine (1 L), dried over sodium sulfate, and concentrated underreduced pressure. The resulting residue was dissolved in 500 mL oftoluene and p-toluenesulfonic acid (5.6 g, 29.4 mmol, 0.2 equiv) wasadded. This mixture was refluxed for 20 h while removing water with aDean-Stark trap. The reaction was cooled to room temperature andconcentrated under reduced pressure. The resulting residue was purifiedover silica gel (1 Kg), eluting with heptanes to give compound 9 (39 g,75% yield) as a light yellow solid.

4-([1,1′-Biphenyl]-2-yl)-2-cyclopropyl-1H-indene (10)

A solution of compound 9 (10 g, 28.8 mmol, 1 equiv) and anhydroustoluene (100 mL) was treated withbis(triphenylphosphine)-palladium(II)dichloride (2.35 g, 2.9 mmol, 0.1equiv). After stirring for 10 minutes, 0.5 M cyclopropylmagnesiumbromide in tetrahydrofuran (300 mL, 149.7 mmol, 5.2 equiv) was addeddropwise. The reaction was heated at 60° C. overnight. Additionalbis(triphenylphosphine)-palladium(II)dichloride (2.35 g, 2.9 mmol, 0.1equiv) was added and the reaction heated at 60° C. for an additional 24hours. The reaction was concentrated under reduced pressure and theresidue partitioned between water (1 L) and ethyl acetate (1 L). Thelayers were separated and the aqueous layer washed with ethyl acetate (1L). The combined organic layers were washed with saturated brine (1 L),dried over sodium sulfate, and concentrated under reduced pressure. Theresulting residue was purified over silica gel (200 g) eluting withheptanes to give compound 10 (3.3 g, 37% yield) as a light yellow oil.

Lithium [1-(4-o-biphenyl-2-cyclopropylindenide)]

A solution of 7-o-biphenyl-2-cyclopropyl-indene (2.538 g, 8.229 mmol) indiethyl ether (40 mL) was precooled at −35° C. for 0.5 h. nBuLi (2.5 M,3.3 mL, 8.25 mmol) was added. The solution was stirred at roomtemperature for 18 h. All volatiles were evaporated. The yellow solidwas washed with pentane (5 mL twice, 10 mL once) and dried under vacuumto give the lithium compound (2.11 g).

Lithium {1-[4-(3,5-di-tert-butylphenyl)-2-methyl indenide]}

A solution of 7-(3,5-di-tert-butylphenyl)-2-methyl-indene (5.46 g, 17.14mmol) in diethyl ether (50 mL) was precooled at −35° C. for 0.5 h. nBuLi(2.5 M, 7 mL, 17.5 mmol) was added. The solution was stirred at roomtemperature for 17 h. All volatiles were evaporated. The residue waswashed with hexane (10 mL×4) and dried under vacuum to give the crudeproduct (5.7 g).

Chlorodimethyl[4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl]silane

A solution of the above crude product (1.4 g, 4.315 mmol) in diethylether (20 mL) was precooled at −35° C. for 30 min. Me2SiCl2 (8 g, 61.99mmol) was added and the white slurry was stirred at room temperature for17 h. All volatiles were evaporated. The residue was extracted withpentane (20 mL) and the filtrate was concentrated to dryness undervacuum to give the product (1.74 g, 98%).

Dimethylsilyl[4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl]trifluoromethanesulfonate

A solution ofchlorodimethyl[4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl]silane (1.71g, 4.16 mmol) in toluene (10 mL) was added to a solution of silvertrifluoromethanesulfonate (1.1 g, 4.28 mmol) in toluene (5 mL) withstirring. The white slurry was stirred at room temperature for 3 h.Toluene was removed under vacuum and the residue was extracted withpentane (25 mL). The pentane filtrate was concentrated under vacuum togive the product (1.88 g).

(4-o-Biphenyl-2-cyclopropyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)dimethylsilane

A precooled solution ofdimethylsilyl[4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl]trifluoromethanesulfonate(0.71 g, 1.353 mmol) in diethyl ether (10 mL) was added to a precooledmixture of lithium [1-(4-o-biphenyl-2-cyclopropyl indenide)](0.435 g,1.384 mmol) in diethyl ether (20 mL). The solution was stirred at roomtemperature for 17 h. Diethyl ether was evaporated. The residue wasextracted with pentane (30 mL) and the pentane filtrate was concentratedunder vacuum to give the crude product as a white solid (0.9 g).

Dilithium dimethylsilyl(4-o-biphenyl-2-cyclopropylindenide)(4-(3,5-di-tert-butylphenyl)-2-methyl indenide)

nBuLi (2.5 M, 1 mL, 2.5 mmol) was added to a precooled solution of theabove product (0.86 g, 1.259 mmol) in diethyl ether (25 mL). Thesolution was stirred at room temperature for 22 h. All volatiles wereremoved under vacuum. The residue was washed with pentane (10 mL×2) anddried under vacuum to give the dilithium compound as an Et2O adduct(0.915 g).

Dimethylsilyl(4-o-biphenyl-2-cyclopropyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)zirconiumdichloride

A precooled solution of the above [dilithium dimethylsilyl(4-o-biphenyl-2-cyclopropyl indenide)(4-(3,5-di-tert-butylphenyl)-2-methyl indenide)][Et2O](0.9 g, 1.17 mmol)in Et2O (15 mL) was added to a precooled slurry of ZrCl4 (0.275 g, 1.18mmol) in Et2O (15 mL). The mixture was stirred at room temperature for20 h. The solution was evaporated to dryness. The residue was washedwith pentane (15 mL once and 5 mL once) and then extracted with toluene(20 mL). The toluene filtrates were evaporated to dryness and washedwith diethyl ether and then pentane to afford 0.11 g (11%) of themetallocene with a rac/meso-ratio of 5:1. The product was further washedwith diethyl ether to give 0.04 g (4.1%) of dimethylsilyl (4-O—biphenyl-2-cyclopropyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)zirconiumdichloride with a rac/meso ratio of 33:1. ¹H NMR (400 MHz, CD2Cl2, 23°C.): rac: δ 7.67 (m, 1H), 7.59 (m, 2H), 7.4 (m, 6H), 7.33 (m, 1H), 7.15(m, 1H), 7.08 (m, 5H), 7.01 (m, 1H), 6.96 (m, 1H), 6.85 (s, 1H), 6.00(s, 1H), 2.22 (s, 3H), 1.89 (m, 1H), 1.34-1.32 (tBu×2 overlapped withSiMe2, 24H), 0.94 (m, 1H), 0.73-0.60 (m, 2H), 0.15 (m, 1H).Characteristic ¹H NMR chemical shifts for meso: δ 5.83 (s, 1H), 2.38 (s,3H), 1.90 (m, 1H), 1.46 (s, 3H, SiMe), 1.33 (s, 18H, tBu×2), 1.23 (s,3H, SiMe).

Supported Dimethylsilyl(4-o-biphenyl-2-cyclopropyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl)ZirconiumDichloride (Catalyst 3)

In a 20 mL vial the metallocene (19.4 mg, 0.0230 mmol) was stirredalongside MAO (30% by weight in toluene, 0.2125 g of solution) alongwith another 2 mL of toluene for 1 h. In a small celstir SMAO (preparedas described above) (0.5747 g) was slurried in 20 mL of toluene. Thecelstir was chilled for 1 min in the freezer (−35° C.) before thecatalyst solution is added to the slurry. The slurry was stirred for 1 hwhile spending 1 min of every 10 min in the freezer. The slurry was thenheated to 40° C. and stirred for 2 h. The slurry was then filtered usinga fine glass frit, reslurried in 20 mL of toluene and stirred for anadditional 30 min at 60° C. The slurry was then filtered, reslurried in20 mL of toluene and stirred for an additional 30 min at 60° C. Theslurry was then filtered, reslurried in 20 mL of toluene and stirred foran additional 30 min at 60° C. and then filtered for the final time. Thecelstir was washed out with 20 mL of toluene and the solid was driedunder vacuum. Collected 0.5044 g of pink solid.

Supported rac-Dimethylsilyl Bis(2-methyl-4-phenyl-indenyl)ZirconiumDichloride (Catalyst-1)

In a 20 mL the metallocene (23.3 mg, 0.0396 mmol) was stirred alongsideMAO (30% by weight in toluene, 0.3278 g of solution) along with another2 mL of toluene for 1 h. In a small celstir S*MAO (prepared as describedbelow) (0.9915 g) was slurried in 20 mL of toluene. The catalystsolution was added to the slurry. The slurry stirred for 1 h. The slurrywas then filtered using a fine glass frit, washed four times with 20 mLof toluene, and the red solid was dried under vacuum. Collected 0.9639 gof red solid. The S*MAO is typically prepared as follows: In a celstir,MS-3050 silica (600° C. calcined, 8.8627 g) was slurried in 90 mL oftoluene. MAO (25.9320 g of a 30% wt toluene solution) was added slowlyto the slurry. The slurry was stirred at room temperature for 1 h andthen 80° C. for 20 min. Reaction monitoring via NMR showed high MAOuptake. An additional 2.8644 g of the MAO solution was added to theslurry and stirred for another 20 min. NMR analysis showed fullsaturation of silica by the MAO. The slurry was filtered with a glassfrit filter and washed three times with 25 mL of toluene and one timewith 40 mL of toluene. The solid was dried under vacuum for 24 h.15.0335 g of a free flowing white solid were collected.

Characterization

Gel Permeation Chromatography-DRI (GPC-DRI)

Mw, Mn and Mw/Mn are determined by using a High Temperature GelPermeation Chromatography (Polymer Laboratories), equipped with adifferential refractive index detector (DRI). Three Polymer LaboratoriesPLgel 10 μm Mixed-B columns are used. The nominal flow rate is 1.0mL/min, and the nominal injection volume is 300 μL. The various transferlines, columns, and differential refractometer (the DRI detector) arecontained in an oven maintained at 160° C. Solvent for the experiment isprepared by dissolving 6 grams of butylated hydroxytoluene as anantioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1μm Teflon filter. The TCB is then degassed with an online degasserbefore entering the GPC instrument. Polymer solutions are prepared byplacing dry polymer in glass vials, adding the desired amount of TCB,then heating the mixture at 160° C. with continuous shaking for about 2hours. All quantities are measured gravimetrically. The injectionconcentration is from 0.5 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector is purged. Flow rate in the apparatus is then increasedto 1.0 ml/minute, and the DRI is allowed to stabilize for 8 hours beforeinjecting the first sample. The molecular weight is determined bycombining universal calibration relationship with the column calibrationwhich is performed with a series of monodispersed polystyrene (PS)standards. The MW is calculated at each elution volume with followingequation.

${\log\; M_{X}} = {\frac{\log\left( {K_{X}\text{/}K_{PS}} \right)}{a_{X} + 1} + {\frac{a_{PS} + 1}{a_{X} + 1}\log\; M_{PS}}}$where the variables with subscript “X” stand for the test sample whilethose with subscript “PS” stand for PS. In this method, a_(PS)=0.67 andK_(PS)=0.000175 while a_(X) and K_(X) are obtained from publishedliterature. Specifically, a/K=0.695/0.000579 for PE and 0.705/0.0002288for PP.

The concentration, c, at each point in the chromatogram is calculatedfrom the baseline-subtracted DRI signal, IDRI, using the followingequation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. Specifically,dn/dc=0.109 for both PE and PP.

The mass recovery is calculated from the ratio of the integrated area ofthe concentration chromatography over elution volume and the injectionmass which is equal to the pre-determined concentration multiplied byinjection loop volume.

All molecular weights are reported in g/mol unless otherwise noted.

Melt Flow Rate (MFR)

MFR was measured as per ASTM D1238, condition L, at 230° C. and 2.16 kgload.

Differential Scanning Calorimetry (DSC)

Peak crystallization temperature (Tc) and peak melting temperature (Tm)was measured via Differential Scanning Calorimetry (DSC) using a DSCQ200unit. The sample was first equilibrated at 25° C. and subsequentlyheated to 220° C. using a heating rate of 10° C./min (first heat). Thesample was held at 220° C. for 3 min. The sample was subsequently cooleddown to −100° C. with a constant cooling rate of 10° C./min (firstcool). The sample was equilibrated at −100° C. before being heated to220° C. at a constant heating rate of 10° C./min (second heat). Theexothermic peak of crystallization (first cool) was analyzed using theTA Universal Analysis software and the corresponding to 10° C./mincooling rate was determined. The endothermic peak of melting (secondheat) was also analyzed using the TA Universal Analysis software and thepeak melting temperature (Tm) corresponding to 10° C./min heating ratewas determined. Areas under the DSC curve are used to determine the heatof transition (heat of fusion, Hf, upon melting or heat ofcrystallization, He, upon crystallization), which can be used tocalculate the degree of crystallinity (also called the percentcrystallinity). The percent crystallinity (X %) is calculated using theformula: [area under the curve (in J/g)/H° (in J/g)]*100, where H° isthe ideal heat of fusion for a perfect crystal of the homopolymer of themajor monomer component. These values for H° are to be obtained from thePolymer Handbook, Fourth Edition, published by John Wiley and Sons, NewYork 1999, except that a value of 290 J/g is used for H° (polyethylene),a value of 140 J/g is used for H° (polybutene), and a value of 207 J/gis used for H° (polypropylene).

Secant Flexural Modulus

1% secant flexural modulus) was measured using a ISO 37-Type 3 bar, witha crosshead speed of 1.0 mm/min and a support span of 30.0 mm using anInstron machine according to ASTM D 790 (A, 1.0 mm/min).

Size Exclusion Chromatography

In conducting the ¹³C NMR investigations, samples were dissolved ind2-1,1,2,2-tetrachloroethane at concentrations between 10 to 15 wt % ina 10 mm NMR tube. ¹³C NMR data was collected at 120° C. using a Varian400 spectrometer with a 1H frequency of at least 400 MHz. A 90 degreepulse, an acquisition time adjusted to give a digital resolution between0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating was employed during the entire acquisitionperiod. The spectra were acquired using time averaging to provide asignal to noise level adequate to measure the signals of interest.

EXAMPLES

Catalyst 1 is silica supported Me2Si(2-Me-4-Ph-Ind)2ZrCl2.

Catalyst 2 is silica supported Me2Si(2-cPr-4-(3′,5′-tBu2-Ph)-Ind)2ZrCl2)

Polymerizations

The propylene polymerization reactions were carried out under stagedhydrogen addition conditions (e.g. No H2 in first 40 minutes of thereactor run then using various pressures of H2 in the next 20 minutes ofthe reactor run). This produced broad/bi-modal MWD iPP with excellentstiffness properties in the MFR (50 dg/min or more).

General Procedure for Reactor Propylene Polymerization UsingSilica-Supported Catalysts Procedure 1

Supported catalyst (ca. 0.6 g) (Catalyst-1 or Catalyst-2) was slurriedinto dry HYDROBRITE™ oil to yield a slurry that contains 5% by weight ofthe supported catalyst. A catalyst slurry containing the supportedcatalysts (see Table 1) was injected using 250 ml propylene into a 2 Lautoclave reactor containing propylene (1000 mL) (total propylene 1250ml), H2 (provided from a 183 mL container), and tri-n-octylaluminum, 1.0mls of a 4.76 vol % hexane solution, at room temperature for 5 minutes.Subsequently, the reactor temperature was raised to the run temperaturefor 30 to 50 minutes. After the allotted time the reactor was cooled toroom temperature and vented.

Procedure 2

The procedure above was followed except that after the 30-50 minutes thereactor was not cooled and vented. Instead, hydrogen (provided from a183 mL container) was added into the reactor at a desired loading toeffect chain termination. After the 10-15 minutes the reactor was cooledto room temperature, vented, and the resulting polymer was removed fromthe reactor. Under this procedure it is noted that the cooling andventing procedure allows exposure of the reaction to hydrogen to extendfor approximately 10 to 20 minutes.

Procedure 3

Supported catalyst (ca. 0.6 g) (Catalyst-1 or Catalyst-2) was slurriedinto dry HYDROBRITE™ oil to yield a slurry that contains 5% by weight ofthe supported catalyst. A catalyst slurry containing certain amounts ofcatalysts (see Table 1) was injected using 250 ml propylene into a 2 Lautoclave reactor containing propylene (1000 mL) (total propylene 1250ml), and tri-n-octylaluminum, 1.0 mls of a 4.76 vol % hexane solution,at room temperature for 5 minutes. Subsequently, the reactor temperaturewas raised to the run temperature for an allotted period of time. Afterthe time indicated in Table 1 time H2 (provided from a 183 mL container)was added into the reactor at a desired loading to effect chaintermination. After the allotted time the reactor was immediately ventedand reactor was allowed to cool to room temperature.

TABLE 1 Propylene Polymerization Using Silica-Supported Catalysts at 70°C. Amount of oil Stage 1 Stage 2 1% Secant Exam- slurry containing H₂(mmols)/ H₂ (mmols)/ MFR Activity flexural ple Catalyst catalystProcedure run time (min) run time (min) dg/min Yield (g) (g P/g sup.cat)M_(n) (kg/mol) M_(w) (kg/mol) M_(w)/M_(n) modulus (MPa) Tm (° C.) Tc (°C.) 1 1 0.209 1 2.07/50   NA 0.16 21.1 2019 1676 2 1 1.15 1 10.3/50   NA26 123 2139 29.2 205.6 7.0 1378 3 1 1.16 1 11.9/50   NA 59 110 1897 29.6157.7 5.3 1427 4 1 1.15 1 12.9/50   NA 74 136 2365 29.5 191.4 6.5 1453 51 1.16 1 15.5/50   NA 138 124 2138 20.3 115.7 5.7 1464 6 1 1.06 2  0/5023.8/10 75 63.9 1206 20.0 207.9 10.4 1621 149.4 113.3 7 1 1.25 3  0/5015.5/10 0.37 20.2 323 80.9 498.5 6.2 1601 150.2 113.1 8 1 1.06 3  0/3023.8/10 4.1 41.9 791 21.3 438.4 20.5 1577 150.5 113.1 9 1 1.06 3  0/3023.8/10 37 43.5 821 20.5 500.5 24.4 1640 150.4 112.9 10 1 1.05 3  0/3023.8/15 63 57.3 1091 18.5 322.3 17.5 1571 149.9 114.1 11 2 1.22 1  0/40NA 2.5 46.3 759 102.2 350.8 3.4 1576 154.4 112.4 12 2 1.20 1 3.62//50 NA42 169.4 2823 46.3 167.4 3.6 1255 153.8 113.1 13 2 1.21 1 4.65/50   NA63 180.5 2983 47.0 148.7 3.2 1327 153.8 112.7 14 2 1.20 1 7.24/50   NA181 205.7 3428 31.6 116.0 3.7 1202 154.1 114.3 15 2 1.21 2  0/40 15.5/10107 124 2050 24.9 188.6 7.6 1695 153.8 116.5 16 2 1.21 3  0/40 15.5/1053 103 1702 25.5 194.0 7.6 1740 153.8 115.4 17 2 1.22 2  0/40 21.7/10820 120.6 1977 11.4 124.7 11 1971 153.2 117.1 18 2 1.22 2  0/30 22.7/10834 134.7 2208 11.6 88.3 7.6 1999 153.6 119.5 19 3 0.760 1 9.3/50  NA147 188 4947 38.3 136.5 3.6 1272 152.8 114.5 20 3 0.765 1 14.5/50   NA417 205 5359 26.4 100.9 3.8 1234 153.0 112.9 21 3 0.763 3  0/30 15.5/10105 54.8 1436 21.5 318.2 14.8 1649 153.1 113.7 22 3 0.760 1 5.17/50   NA35 124 3263 50.1 205.8 4.1 1191 154.0 114.0 23 3 0.770 3  0/30 18.1/10138 49.7 1291 20.1 330.3 16.5 1618 153.0 115.8 24 3 0.770 3  0/3013.4/10 46 47.3 1229 22.4 331.7 14.8 1686 153.3 114.0 Exam- Stage 1Stage 2 Stereo Defects 2,1 e Defects 3,1 Defects ple Catalyst H₂(mmols)/time (min) H₂ (mmols)/time (min) [mmmm] (per 10,000 monomers)(per 10,000 monomers) (per 10,000 monomers) Avg. meso Run Length 6 10/50 23.8/10 0.9669 75 95 4 57 15 2 0/40 15.5/10 0.9793 51 54 10 87*mmoles H₂ estimated using ideal gas law assuming room temperature ~293K and volume of hydrogen addition 0.183 L at desired pressure rangingfrom 0.1 atm. to 4 atm. Catalyst 1 is silica supportedMe₂Si(2-Me-4-Ph-Ind)₂ZrCl₂; Catalyst 2 is silica supportedMe₂Si(2-cPr-4-(3′,5′-tBu₂-Ph)-Ind)₂ZrCl₂); Catalyst 3 is supporteddimethylsilyl (4-o-biphenyl-2-cyclopropyl-indenyl)(4-(3,5-di-tert-butylpheny1)-2-methyl-indenyl) zirconium dichloride.

Capillary rheology of selected polymers was conducted according to ASTMD3835-02 on an Alpha Technologies™ ARC 2020 capillary rheometer usingdie Y400-30RC (nominally 1 mm diameter, 30.5 mm length and 90° entryangle) at 190° C. The rheometer was packed and allowed to come tothermal equilibrium for 120 seconds prior to initiating the test.Rabinowitch correction was performed as described at B. Rabinowitsch, Z.Physik. Chem., A 145, 1 (1929) using software program LAB KARS AdvancedRheology Software version 3.92 available from Alpha TechnologiesServices, Akron, Ohio. The Rabinowitch corrected shear viscosity(“RCSV”) data is shown in Table A below.

TABLE A Example 6 Example 15 Example 16 Example 4 Shear RCSV RCSV RCSVRCSV Rate (1/s) (Pa · s) (Pa · s) (Pa · s) (Pa · s) 1 2284.05 866.93238.65 1760.4 2.5 784.3 588.95 1225.2 1087.45 5 408.65 342.9 612.35663.15 7.5 329.2 242.05 477.85 469.45 10. 313.1 189.95 429.1 377.4 25292.05 116.45 330.3 217.2 50 252.2 116.55 247.75 206.55 75 219.65 126.95201.05 249.45 100 200.05 113.3 173.8 227.45 250 134.35 75 104.5 153.25500 93.65 52.35 68.5 88 750 73.9 41.75 53.05 78 1000 62.45 35.45 44.7566.05 1500 48.75 28.35 35.2 45.35 2000 41 24.1 29.7 42.2

TABLE B Comparison of the Rabinowitch corrected shear viscosities RCSV,at RCSV, at Ratio of RCSV 1% Secant Mw/Mn 1 sec⁻¹ 2000 sec⁻¹ at 1sec⁻¹:2000 flexural modulus Example GPC-DRI MFR (dg/min) (Pa · sec) (Pa· sec) sec⁻¹ (MPa) 15 Bimodal 107 866.9 24.1 36 1695 16 Bimodal 533238.65 29.7 109 1740 6 Bimodal 75 2284.05 41 56 1621 4 Unimodal 741760.4 42.2 42 1453

The Rabinowitch corrected shear viscosities at low shear rates in TableA are appreciably distinct, varying from 866 to 3238 Pa·sec, presumablyreflecting a variation in melt strength and bulk physical properties.

Similar viscosities at the high shear rates probed by capillary rheologyconfirm similar processability under environments similar to commercialprocessing equipment. Thus, capillary rheology confirms the utility ofexisting commercial processing equipment to extract the performancebenefits resulting from utilizing the inventive process describedherein.

A direct comparison of comparative unimodal molecular weightdistribution iPP (Example 4) versus bimodal molecular weightdistribution iPP resulting from the inventive process (Example 6) at lowand high shear rates is provided in Table B. This data confirms thehigher viscosity of the bimodal iPP at low shear rates, as well as lowerviscosity than a unimodal iPP of similar MFR at shear rates encounteredduring processing.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related application and/or testing procedures tothe extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is not incorporated by reference herein. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A process to polymerize propylene comprising: 1)contacting propylene, optionally with a comonomer, with a catalystsystem comprising an activator and a catalyst compound represented bythe formula:

where: M is a group 4 metal; T is a bridging group; X is an anionicleaving group; each R³, R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², and R¹³ isindependently, hydrogen, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;each R² and R⁸ is independently, a halogen atom, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,silylcarbyl, substituted silylcarbyl, germylcarbyl, substitutedgermylcarbyl substituents or a —NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkyl group, or aC₆-C₁₀ aryl group; R⁴ and R¹⁰ are, independently, a substituted orunsubstituted aryl group; 2) polymerizing the propylene and optionalcomonomer for a time period, A; 3) adding hydrogen or other chaintermination agent and optional comonomer to the polymerization aftertime period A; 4) polymerizing in the presence of at least 1 mmolhydrogen per mol of propylene for a time period, B, where time period Ais at least as long as time period B and the hydrogen concentrationduring time period B is at least three times greater than the hydrogenconcentration in time period A; and 5) obtaining a propylene polymercomposition having: a) at least 50 mol % propylene; b) a 1% secantflexural modulus of at least 1500 MPa; c) an Mw/Mn of at least 5; d) amelt flow rate of 50 dg/min or more (230° C., 2.16 kg); e) a multimodalmolecular weight distribution; and f) more than 15 and less than 200regio defects (sum of 2,1-erythro and 2,1-threo insertions and3,1-isomerizations) per 10,000 propylene units.
 2. The process of claim1, wherein M is titanium, zirconium or hafnium.
 3. The process of claim1, wherein X is Cl or Me.
 4. The process of claim 1, wherein R⁴ and R¹⁰are, independently, a substituted or unsubstituted phenyl group.
 5. Theprocess of claim 1, wherein the propylene polymer composition containsat least 70 mol % propylene.
 6. The process of claim 1, wherein the meltflow rate of the propylene polymer composition is from about 60 to about100 dg/min.
 7. The process of claim 1, wherein R² and R⁸ are,independently, a halogen atom, a C₁-C₁₀ alkyl group which may behalogenated, a C₆-C₁₀ aryl group which may be halogenated, a C₂-C₁₀alkenyl group, a C₇-C₄₀ -arylalkyl group, a C₇-C₄₀ alkylaryl group, aC₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂ radical,wherein R′ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀aryl group.
 8. The process of claim 1, wherein R⁴ and/or R¹⁰ is a phenylgroup substituted at the 3′ and 5′ positions, independently, with aC₁-C₁₀ alkyl group.
 9. The process of claim 1, wherein R² and R⁸ are,independently, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,nonyl, decyl, undecyl, dodecyl, or isomers of mixtures thereof.
 10. Theprocess of claim 1, wherein R⁴ and R¹⁰ are, independently, an arylgroup, substituted with another group at the ortho position.
 11. Theprocess of claim 10, wherein R⁴ and R¹⁰ are both biphenyl groups. 12.The process of claim 1, wherein the propylene polymer compositionproduced is isotactic.
 13. The process of claim 1, wherein the propylenepolymer composition produced has an mm triad tacticity index of about75% or greater.
 14. The process of claim 1, wherein the polymerizationsof time period A and time period B occur in the same reaction zone. 15.The process of claim 1, wherein the polymerizations of time period A andtime period B occur in different reaction zones.
 16. The process ofclaim 1, wherein time period A is at least 1.5 times longer than timeperiod B.
 17. The process of claim 1, wherein the activator comprises analumoxane.
 18. The process of claim 1, wherein the activator comprises anon-coordinating anion activator.
 19. The process of claim 1, whereinthe catalyst is supported.
 20. The process of claim 1, wherein theprocess is a slurry process.
 21. The process of claim 1, wherein theprocess is a gas phase process.
 22. The process of claim 1, wherein theprocess is a homogeneous process.
 23. The process of claim 1, wherein R²is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, orsubstituted germylcarbyl substituent; R⁴ is an aryl group substituted atthe ortho position with another aryl group or by a linker group, whereinthe linker group is an alkyl, vinyl, phenyl, alkynyl, silyl, germyl,amine, ammonium, phosphine, phosphonium, ether, thioether, borane,borate, alane or aluminate group; R⁸ is a halogen atom, a C₁-C₁₀ alkylgroup which may be halogenated, a C₆-C₁₀ aryl group which may behalogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ -arylalkyl group, a C₇-C₄₀alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′,—OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀alkyl group, or a C₆-C₁₀ aryl group; and R¹⁰ is phenyl group substitutedat the 3′ and 5′ positions, independently, with a C₁-C₁₀ alkyl group.24. A process to produce a propylene impact copolymer comprising: 1)contacting propylene (and optional comonomer) with a catalyst systemcomprising an activator and a catalyst compound represented by theformula:

where: M is group 4 metal; T is Si, Ge, or C; R¹⁴ and R¹⁵ are C₁-C₁₀alkyl and can form a cyclic group; X is an anionic leaving group; eachR², R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², and R¹³ is independently,hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, orsubstituted germylcarbyl substituents, provided that R² and R⁸ is nothydrogen; R⁴ and R¹⁰ are, independently, a substituted or unsubstitutedaryl group; 2) polymerizing the propylene and optional comonomer for atime period, A; 3) adding hydrogen or other chain termination agent andcomonomer to the polymerization after time period A; 4) polymerizing inthe presence of at least 1 mmol of hydrogen per mol of propylene for atime period, B, where time period A is at least as long as time period Band the hydrogen concentration during time period B is at least threetimes greater than the hydrogen concentration in time period A; 5)adding comonomer comprising ethylene and/or a C₄-C₄₀ olefin monomer tothe polymerization after time period B for a time period, C; and 6)obtaining a propylene polymer composition having: a) at least 50 mol %propylene and at least 1 mol % comonomer; b) a 1% secant flexuralmodulus of at least 1500 MPa; c) an Mw/Mn of at least 5; d) a melt flowrate of 50 dg/min or more (230° C., 2.16 kg); e) a multimodal molecularweight distribution; f) more than 15 and less than 200 regio defects(sum of 2,1-erythro and 2,1-threo insertions and 3,1-isomerizations) per10,000 propylene units; and g) a CDBI of 50% or more.
 25. The process ofclaim 24, where the comonomer added to the polymerization after timeperiod B is selected from ethylene and a C₄-C₄₀ olefin monomers.
 26. Theprocess of claim 1, wherein the propylene polymer composition has a Tcof 115° C. or more.
 27. The process of claim 1, wherein the propylenepolymer composition has an RCSV ratio (1 sec⁻¹ to 2000 sec⁻¹) of Y ormore, where Y=38000X^(−1.559), and X is the melt flow rate in dg/min ofthe propylene polymer.